• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    RECHARGEABLE LITHIUM BATTERY AND ELECTRODE AND ELECTROLYTE COMPOSITIONS FOR RECHARGEABLE LITHIUM BATTERY A rechargeable lithium battery (100; 1) includes a compound represented by Chemical Formula 1: Chemical Formula 1 In Chemical Formula 1, each of k , 1, em is 1 O independently an integer from 0 to 20, n is an integer from 1 to 7, and k, 1 em are selected such that the compound of Chemical Formula 1 has an asymmetric structure, that is, k, 1 in are different from each other. The compound of Formula Chemical 1 can be included in the positive electrode (114; 3), negative electrode (112; 2), or in the electrolyte of the rechargeable lithium battery 15 (100; 1).
    公开号:BR102013018778B1
    申请号:R102013018778-0
    申请日:2013-07-23
    公开日:2020-06-30
    发明作者:Seung Bum Suh；Ho-Seok Yang；Maeng-Eun Lee；Dai In Park；Jee- Won Kang；Jin-Hyunk Lim；Hee-Yeon Hwang；Yun-Hee Kim；Kyeong-Beom Cheong；Seon-Hong Lee；Ho-Gon You；Alexey Kashaev；Dae-Yup Shin
    申请人:Samsung Sdi Co., Ltd.；
    IPC主号:
    专利说明:

    [0001] [001] This application claims priority to and the benefit of US Provisional Application N 61 / 698,311 filed with the United States Patent and Trademark Office on September 7, 2012 and US Application Number ⍛ 13 / 830,119 filed with the U.S. Patent United and Trademark Office on March 14, 2013, the entire contents of which are hereby incorporated by reference. FUNDAMENTALS 1. Technical field
    [0002] [002] This disclosure refers to a rechargeable lithium battery having a compound that provides improved thermal impact durability. 2. Description of the Related Art
    [0003] [003] Recently, portable electronic devices (such as cell phones, portable computers, tablets, and the like) are becoming smaller and lighter, increasing the demand for high capacity batteries as energy sources. In response to this demand, rechargeable non-aqueous electrolyte lithium batteries using non-aqueous electrolytes and transporting lithium ions between positive and negative electrodes have been widely used as rechargeable batteries having high strength and high energy density. As the positive active material, the rechargeable non-aqueous electrolyte lithium battery uses an oxide capable of intercalating lithium ions, such as those manufactured from lithium and transition elements, for example, LiCoO2, LiMn 2 O 4 , LiNi 1 - x Co x O2 (0 <x <1), and the like. As the negative active material, the rechargeable non-aqueous electrolyte lithium battery can include artificial or natural graphite for interleaving / deinterleaving lithium, a carbon-based material such as hard carbon, or a material capable of bonding with lithium (such as Si , Sn, or the like), and the like. However, the use of portable electronic devices to run movies, games, and the like is increasing, and the devices tend to consume more electricity when used for these tasks. Thus, portable electronic devices require batteries with high capacity as power sources. The non-aqueous electrolyte rechargeable lithium battery can achieve high capacity 1) by increasing the capacity of an active material, 2) by increasing the charge voltage, 3) by increasing the amount of charge in the active material and thus, charge density, and the like. However, these methods have certain challenges, for example, the method of increasing the charge voltage of an active material breaks down the electrolyte. In particular, when the active material is stored at high temperatures, or is continuously charged, the electrolyte can be decomposed and generate gas, thereby expanding the battery or increasing the internal pressure of the battery. Consequently, attempts to ensure the safety of the battery have been continuously made using an additive to increase the flash point and delay burning, and to decrease changes in thickness, thus improving durability in thermal impact.
    [0004] [004] Conventionally, PS (1,3-propane sultone) has been used as an additive to improve the durability of rechargeable lithium batteries against thermal impact. PS is known to improve the thermal safety of the rechargeable lithium battery, and thus the retention of capacity at high temperatures. However, PS is a toxic material that can cause cancer. In general, a thermal impact test is performed by heating and cooling a battery 30 times from 80 ° C to -40 ° C for one hour to apply voltage. When the battery is allowed to stand at room temperature after applying voltage, and then registers a change in thickness that is less than or equal to a predetermined pattern, the battery is considered to have thermal impact safety. SUMMARY
    [0005] [005] An embodiment of the present invention provides a rechargeable lithium battery having improved thermal impact durability. The rechargeable lithium battery of this invention includes a compound represented by the following Chemical Formula 1:
    [0006] [006] In Chemical Formula 1, each of k, 1, and m is independently an integer from 0 to 20, and k, 1 and m are selected such that the compound of Formula Chemical 1 has an asymmetric structure. As used here, the term "asymmetric structure" means that the compound of Formula Chemical 1 is asymmetric over the central carbon atom (ie, the central carbon atom represented in the general formula of Chemical Formula 1). In some embodiments, k, 1 and m are different from each other. In Chemical Formula 1, n is an integer from 1 to 7. For example, in Chemical Formula 1, n can be 1 to 5, ek, 1, and m can all be different from each other and can all be independently whole numbers of 0 to 10. In another example, in Chemical Formula 1, n can be 1 to 3, k and 1, and m can all be different from each other and can all be independently whole numbers from 0 to 7. In yet another example , in Chemical Formula 1, n can be 1 or 2, k can be 0, and 1 in can be different from each other and can be independently whole numbers from 1 to 5. In yet another example, in Chemical Formula 1, n it can be 1, k it can be 0, 1 it can be 2, and it can be 3. In an exemplary embodiment, the compound represented by Chemical Formula 1 can be HTCN (hexane tri-cyanide). For example, the compound represented by Chemical Formula 1 can be 1,3,6-hexane tri-cyanide, or 1,2,6-hexane tri-cyanide.
    [0007] [007] The compound represented by Chemical Formula 1 can be included in a positive electrode for a rechargeable lithium battery. The compound represented by Chemical Formula 1 can be included in an electrolyte for a rechargeable lithium battery. The compound represented by Chemical Formula 1 can be included in a negative electrode for a rechargeable lithium battery. The compound represented by Chemical Formula 1 can be included in the positive electrode, negative electrode or electrolyte in an amount of 0.1 to 50%, for example 0.1 to 10%, based on the total weight of the positive electrode, negative electrode, or electrolyte, respectively.
    [0008] [008] In another embodiment, an electrode composition for a rechargeable lithium battery includes the compound represented by Chemical Formula 1. The composition can be a positive or negative electrode composition for a rechargeable lithium battery. In yet another embodiment, an electrolyte composition for a rechargeable lithium battery includes the compound represented by Chemical Formula 1. In yet another embodiment, a method of making a rechargeable lithium battery includes preparing an electrode composition to a rechargeable lithium battery and apply the electrode composition to an electrode current collector. Consequently, in an embodiment of the present invention, a rechargeable lithium battery has increased durability in thermal impact and thus, improved safety. BRIEF DESCRIPTION OF THE DRAWINGS
    [0009] [009] The present invention will be better understood by reference to the following detailed description when considered in combination with the accompanying drawings, in which: FIG. 1 is an exploded perspective view of a cylindrical rechargeable lithium battery according to an embodiment; FIG. 2 is a cross-sectional view of a prismatic rechargeable lithium battery according to another embodiment; FIG. 3 is a schematic showing the connection forms of SN (succinonitrile), AN (adiponitrile), and 1,3,6-HTCN (1,3,6-hexane tri-cyanide), respectively, with the surface of a active electrode material; FIG. 4 is a schematic showing the coordination forms of SN (succinonitrile), AN (adiponitrile), and 1,3,6-HTCN (1,3,6-hexane tri-cyanide), respectively, with metal ions ; FIGS. 5 (a) to (c) are schematic showing that the compounds having two or more CN functional groups and a global symmetry structure, i.e. SN (succinonitrile), 1,2,3-PTCN, and 1,3, 5-PTCN, are respectively bonded to the surface of an active electrode material; and FIG. 5 (d) and 5 (e) are a schematic showing that two compounds, 1,3,6-HTCN (1,3,6-hexane tri-cyanide) and 1,2,6-HTCN (tri-cyanide) 1,2,6-hexane), represented by Chemical Formula 1 according to the present invention, are respectively bonded to the surface of an active electrode material. DETAILED DESCRIPTION OF METHODS
    [0010] [0010] Exemplary embodiments of the present disclosure will be described in detail below. However, these embodiments are only exemplary, and this disclosure is not limited to this.
    [0011] [0011] In an embodiment of the present invention, a rechargeable lithium battery includes a compound represented by the following Chemical Formula 1:
    [0012] [0012] In Chemical Formula 1, each of k, 1, and m is independently an integer from 0 to 20, and k, 1 and m are selected such that the compound of Formula Chemical 1 has an asymmetric structure. As used here, the term "asymmetric structure" means that the compound of Formula Chemical 1 is asymmetric over the central carbon atom (ie, the central carbon atom represented in the general formula of Chemical Formula 1). In some embodiments, k, 1 and m are different from each other. In Chemical Formula 1, n is an integer from 1 to 7. For example, in Chemical Formula 1, n can be 1 to 5, ek, 1, and m can all be different from each other and can all be independently whole numbers of 0 to 10. In another example, in Chemical Formula 1, n can be 1 to 3, k and 1, and m can all be different from each other and can all be independently whole numbers from 0 to 7. In yet another example , in Chemical Formula 1, n can be 1 or 2, k can be 0, and 1 in can be different from each other and can be independently whole numbers from 1 to 5. In yet another example, in Chemical Formula 1, n can be 1, k can be 0.1 can be 2, and m can be 3.
    [0013] [0013] In an exemplary embodiment, the compound represented by Chemical Formula 1 can be HTCN (hexane tri-cyanide). For example, the compound represented by Chemical Formula 1 can be 1,3,6-hexane tri-cyanide, or 1,2,6-hexane tri-cyanide.
    [0014] [0014] The compound represented by Chemical Formula 1 can be included in a positive electrode for a rechargeable lithium battery. The compound represented by Chemical Formula 1 can be included in an electrolyte for a rechargeable lithium battery. The compound represented by Chemical Formula 1 can be included in a negative electrode for a rechargeable lithium battery. The compound represented by Chemical Formula 1 above can be included in the positive electrode, negative electrode or electrolyte in an amount of 0.1 to 50%, for example 0.1 to 10%, based on the total weight of the positive electrode, negative electrode or electrolyte, respectively. In general, when rechargeable lithium batteries have a higher capacity (and thus higher energy density), the rechargeable lithium battery tends to become thicker due to deteriorated internal safety against thermal impact. It is important to minimize this change in thickness in the rechargeable lithium battery due to thermal impact, which can determine the thickness of the mobile device (which has been getting thinner and thinner) and prevent the destruction of the mobile device.
    [0015] [0015] According to embodiments of the present invention, a rechargeable lithium battery includes the compound represented by Chemical Formula 1, and thus has a reduced thickness change due to thermal impact, and thus has durability in improved thermal impact and safety in improved thermal impact.
    [0016] [0016] In general, a thermal impact test is performed by heating and cooling a battery 30 times from 80 ° C to -40 ° C for one hour to apply voltage. When the battery is allowed to stand at room temperature after applying voltage, and then registers a change in thickness that is less than or equal to a predetermined pattern, the battery is considered to have thermal impact safety. According to embodiments of the present invention, a rechargeable lithium battery including the compound represented by Formula Chemical 1 has a decreased thickness change after thermal impact (as mentioned in the following examples), and thus has improved safety.
    [0017] [0017] The compound represented by Chemical Formula 1 is a hydrocarbon compound including 3 to 9 CN functional groups, for example 3 to 7 CN functional groups, 3 to 5 CN functional groups, or 3 CN functional groups. Without being bound by any particular theory, due to a coordination link between unshared electron pairs at N at the CN group's terminal end and various metals (such as transition elements and the like) of the positive active material, the compound represented by the Formula Chemistry 1 forms a stable film on the surface of the positive electrode and suppresses a side reaction between the positive electrode and the electrolyte. In addition, the compound is bonded with other materials included in the battery and decomposes the materials and suppresses an exothermic phenomenon, thus suppressing temperature increases in the battery. In addition, the compound is bonded with other materials included in the battery and thus blocks the formation of a black dot on the battery, and suppresses the short circuit due to the extraction on the surface of the negative electrode by metallic impurities.
    [0018] [0018] Consequently, the compound represented by Chemical Formula 1 can be included in any of the positive electrode, negative electrode, or battery electrolyte, and can improve the battery's durability against thermal impact.
    [0019] [0019] As illustrated in the following examples, the compound represented by Chemical Formula 1 (having k, 1, m, en as defined above) has a much lower binding energy with metal ions in the battery and thus forms a more stable bond and stronger than a hydrocarbon compound having only two CN functional groups at the end end, or a similar compound having a symmetrical structure over the center of the compound having a CN functional group at the end end. Consequently, the compound represented by Formula Chemical 1 most dramatically decreases the thickness change in the battery due to thermal impact.
    [0020] [0020] The effect of decreasing a change in thickness can be illustrated with reference to FIGS. 3 to 5. In particular, FIG. 3 is a schematic showing that each SN (succinonitrile), AN (adiponitrile), and 1,3,6-HTCN (1,3,6-hexane tri-cyanide) is bonded to a surface of an active electrode material . Based on the design, 1,3,6-HTCN is more stably bonded to the surface of an active electrode material than SN or AN.
    [0021] [0021] FIG. 4 is a schematic showing that SNs (succinonitriles), ANs (adiponitriles), and 1,3,6-HTCNs (1,3,6-hexane tri-cyanides) have coordinated bonds with a metal ion in the center. As for 1,3,6-HTCNs (as opposed to SN or AN), two compounds (each having three CN functional groups) sterically prevent and are attached to a metal ion in the center. In contrast, as for SNs or ANs, three compounds (each having two CN functional groups) surround a metal ion and have coordinated bonds with the metal ion. However, these compounds bidimensionally (not cubically) surround the metal ion, and have coordinated bonds with the metal ion, unlike 1,3,6-HTCN, represented by Chemical Formula 1 above.
    [0022] [0022] FIG. 5 is a schematic showing that the compounds, SN (succinonitrile), 1,2,3-PTCN (1,2,3-propane tri-cyanide), 1,3,5-PTCN (1, 3,5-pentane), 1,3,6-HTCN (1,3,6-hexane tri-cyanide), and 1,2,6-HTCN (1,2,6-hexane tri-cyanide), are respectively bonded to a surface of an active electrode material. As shown in the following examples 11 to 14, 1,3,6-HTCN having an asymmetric structure shows stronger adsorption on the surface of an active electrode material than 1,2,3-PTCN (1,2-tri-cyanide, 3-propane) or 1,3,5-PTCN (1,3,5-pentane tri-cyanide) having a symmetrical structure between compounds having three CN functional groups. When the compound represented by Formula Chemical 1 is included in a positive electrode or a negative electrode for a rechargeable lithium battery, the compound represented by Formula Chemical 1 can be included in a composition to manufacture the positive electrode or the negative electrode.
    [0023] [0023] In another embodiment of the present invention, an electrode composition for a rechargeable lithium battery includes the compound represented by Chemical Formula 1. The composition can be a positive or negative electrode composition for a rechargeable lithium battery.
    [0024] [0024] In yet another embodiment of the present invention, an electrolyte composition for a rechargeable lithium battery includes the compound represented by Chemical Formula 1.
    [0025] [0025] In yet another embodiment of the present invention, a method of making a rechargeable lithium battery includes preparing an electrode composition for a rechargeable lithium battery and applying the electrode composition to an electrode-type current collector. In accordance with an embodiment of the present invention, a rechargeable lithium battery can be manufactured by any commonly known method using materials known in the related art, except that the compound represented by Formula Chemical 1 is used.
    [0026] [0026] Rechargeable lithium batteries can be classified into lithium ion batteries, lithium ion polymer batteries, and lithium polymer batteries according to the presence of a separator and the type of electrolyte used in the battery. Rechargeable lithium batteries can come in a variety of shapes and sizes, and include cylindrical, prismatic, or coin-type batteries, and can be thin-film batteries or can be preferably large in size. Structures and manufacturing methods for these batteries are known in the art.
    [0027] [0027] Referring to FIG. 1, the rechargeable lithium battery 100 includes a negative electrode 112, a positive electrode 114, and a separator 113 between negative electrode 112 and positive electrode 114. An electrolyte (not shown) impregnates negative electrode 112, positive electrode 114, and separator 113. The battery further includes a battery box 120 and a sealing member 140 for sealing battery box 120. Such a rechargeable lithium battery 100 is manufactured sequentially by stacking negative electrode 112, separator 113, and positive electrode 114, spiraling the battery, and housing the rolled product in the battery box 120.
    [0028] [0028] Referring to FIG. 2, the rechargeable lithium battery 1 includes an electrode assembly including a negative electrode 2, a positive electrode 3, and a separator 4 between the negative electrode 2 and the positive electrode 3. A battery box 5 houses the electrode assembly, an electrolyte is injected into the box from above, and a protective plate 6 seals the battery box 5.
    [0029] [0029] The rechargeable lithium battery can have a cylindrical or prismatic shape, as described above, but is not limited to this, and can have any shape (such as a cylinder, coin, purse, or the like) as long as it include a separator for a rechargeable lithium battery and basically function as a battery. The negative electrode for a rechargeable lithium battery includes a current collector and a layer of negative active material formed in the current collector, and the layer of negative active material includes a negative active material.
    [0030] [0030] The negative active material may include a material that reversibly interleaves / deinterleaves lithium ions, lithium metal, a lithium metal alloy, a material capable of doping / de-doping lithium, or a transition metal oxide. The material that reversibly interleaves / deinterleaves lithium ions can be a carbon material. The carbon material can be any material based on negative active carbon generally used in rechargeable lithium ion batteries. Examples of the carbon material include crystalline carbon, amorphous carbon, and a combination thereof. The crystalline carbon can be natural graphite or artificial graphite without form, or in the form of sheet, flake, spherical, or fiber. Amorphous carbon can be a soft carbon, a hard carbon, a carbonized product of mesophase pitch, burnt coke, or the like.
    [0031] [0031] The lithium metal alloy includes lithium and at least one metal selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge , Al, or Sn. Examples of the lithium doping / de-doping material include Si, SiO x (0 <x <2), a Si-C composite, a Si-Q alloy (where Q is an alkali metal, an alkaline earth metal, an element from Group 13 to 16, a transition element, a rare earth element, or a combination thereof, but not Si), Sn, SnO 2 , a composite of Sn-C, Sn-R (where R is a alkali metal, an alkaline earth metal, a Group 13 to 16 element, a transition element, a rare earth element, or a combination thereof, but not Sn), and the like. Exemplary elements for Q and R include Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh , Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi , S, Se, Te, Po, or a combination thereof.
    [0032] [0032] The transition metal oxide can be vanadium oxide, lithium oxide and vanadium, or the like.
    [0033] [0033] The layer of negative active material can include a binder and optionally also include a conductive material. The binder improves the binding properties of the particles of negative active material with each other and with the current collector. Examples of the binder include polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyethylene fluoride, polyvinyl fluoride, polyethylene fluoride, polyvinyl fluoride, polyvinyl fluoride, polyvinyl fluoride, polyethylene fluoride, polyethylene fluoride, polyvinyl fluoride, polyvinyl fluoride, polyvinyl fluoride, polyvinyl fluoride, polyvinyl fluoride, polyvinyl fluoride, polyvinyl fluoride. acrylated styrene-butadiene rubbers, epoxy resins, nylon, and the like, but are not limited to these.
    [0034] [0034] Conductive material is included to improve the conductivity of the electrode. Any electrically conductive material can be used as a conductive material as long as it does not cause a chemical change. Examples of the conductive material include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene carbon black, ketjen black, carbon fibers, and the like; metal-based materials such as metallic powders or metallic fibers including copper, nickel, aluminum, silver, or the like; conductive polymers such as polyphenylene derivatives; or mixtures of these.
    [0035] [0035] The current collector can be a copper sheet, a nickel sheet, a stainless steel sheet, a titanium sheet, a nickel foam, a copper foam, a polymer substrate coated with a conductive metal, or a combination of them.
    [0036] [0036] The positive electrode of the rechargeable lithium battery includes a current collector and a layer of positive active material disposed in the current collector. The positive active material includes a compound that reversibly interleaves and deinterleaves lithium ions (i.e., a lithium intercalating compound). The positive active material can include a composite oxide including lithium and at least one selected from cobalt, manganese, and nickel. In particular, the following compounds can be used: Li a A 1-b R b D 2 (0.90 ≤ a≤ 1.8 and0≤ b≤ 0.5); LiaEi-bRbCh-cDc (0.90 ≤ a≤ 1.8, 0≤ b≤ 0.5e0≤ c≤ 0.05); LiE 2-b R b O 4-c D c (0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05); Li a Ni 1-bc Co b R c D a (0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 ≤ a ≤ 2); Li a Ni 1-bc Co b R c O 2-a Z a (0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 ≤ a ≤ 2); Li a Ni 1-bc Co b RcO 2-a Z 2 (0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 ≤ a ≤ 2); Li a Ni 1-bc Mn b R c D a (0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 ≤ a ≤ 2); Li a Ni 1-bc Mn b R c O 2-a Z a (0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05 and 0 ≤ a ≤ 2); Li a Ni 1-bc Mn b R c O 2-a Z 2 (0.90 ≤ a ≤ 1.8, 0≤ b≤ 0.5, 0 ≤ c ≤ 0.05 and 0 <a <2); Li a Ni b E c G d O h (0.90 ≤a≤l, 8, 0≤b≤ 0.9, 0 ≤ c ≤ 0.5 and 0.001 ≤ d ≤ 0.1); Li a Ni b Co c Mn d GeO 2 (0.90 ≤ a≤ l, 8, 0≤ b≤ 0.9, 0 ≤ c ≤ 0.5, 0 ≤ d ≤ 0.5, 0.001 ≤ and ≤ 0 ,1); Li a NiG b O 2 (0.90 ≤ a ≤ 1.8 and 0.001 ≤ b ≤ 0.1); Li a CoG b O 2 (0.90 ≤ a ≤ 1.8 and 0.001 <b ≤ 0.1); Li a MnG b O 2 (0.90 ≤ a ≤ 1.8 and 0.001 <b ≤ 0.1); Li a Mn 2 G b O 4 (0.90 ≤ a ≤ 1.8 and 0.001 <b ≤ 0.1); QO 2 ; QS 2 ; LiQS 2 ; V 2 O 5 ; LiV 2 0 5 ; LiTO 2 ; LiNiVO 4 ; Li (3-f) J 2 (PO 4 ) 3 (0 ≤ f ≤ 2); Li (3-f) Fe 2 (PO 4 ) 3 (0 ≤ f ≤ 2); and LiFePO 4 .
    [0037] [0037] In the chemical formulas above, A is Ni, Co, Mn, or a combination thereof. R is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof. D is O, F, S, P, or a combination thereof. And it's Co, Mn, or a combination of them. Z is F, S, P, or a combination of them. G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof. Q is Ti, Mo, Mn, or a combination thereof. T is Cr, V, Fe, Sc, Y, or a combination thereof. J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.
    [0038] [0038] The compound can have a coating layer on the surface or it can be mixed with a compound having a coating layer. The coating layer may include at least one coating element compound selected from oxides of a coating element, hydroxides of a coating element, oxyhydroxides of a coating element, oxycarbonates of a coating element, and hydroxyl carbonates of a cladding element. The compounds for the coating layer can be amorphous or crystalline. The coating element for the coating layer can include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof. The coating layer can be formed by any method as long as there is no negative influence on the properties of the positive active material including the element (s) in the compound. For example, the method can include any coating method such as spray coating, dipping, and the like, which are known to those working in the related field.
    [0039] [0039] The layer of positive active material can include a binder and a conductive material. The binder improves the binding properties of the particles of positive active material to each other and to the current collector. Non-limiting examples of the binder include polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, diacetylcellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polyethylene, polyethylene, polyethylene fluoride styrene-butadiene, acrylated styrene-butadiene rubbers, epoxy resins, nylon, and the like.
    [0040] [0040] The conductive material is used to provide conductivity to the electrode. The conductive material can include any electrically conductive material as long as it does not cause a chemical change. Examples of the conductive material include one or a mixture of a conductive material such as natural graphite, artificial graphite, carbon black, acetylene carbon black , ketjen black , a carbon fiber, a metallic powder, a metallic fiber or the like such as copper, nickel, aluminum, silver or the like, or a derivative of polyphenylene or the like.
    [0041] [0041] The current collector can be Al but is not limited to this one.
    [0042] [0042] The negative and positive electrodes can all be manufactured by mixing the active material, conductive material, and binder to prepare a composition of active material, and coating the composition in a current collector. The electrode manufacturing method is known. The solvent includes N-methylpyrrolidone or the like but is not limited to this.
    [0043] [0043] The electrolyte includes a non-aqueous organic solvent and a lithium salt. The non-aqueous organic solvent serves as a medium to transmit ions that participate in the electrochemical reaction of the battery. The non-aqueous organic solvent can include a carbonate based, ester based, ether based, ketone based, alcohol based, or aprotic solvent. Examples of the carbonate-based solvent can include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methyl ethyl carbonate (MEC) , ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and the like. Examples of the ester-based solvent may include methyl acetate, ethyl acetate, n-propyl acetate, 1,1-dimethylethyl acetate, methyl propionate, ethyl propionate, y-butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone , and the like. Examples of the ether-based solvent include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetetrahydrofuran and tetrahydrofuran. Examples of the ketone-based solvent include cyclohexanone, and the like. Examples of the alcohol-based solvent include ethyl alcohol, isopropyl alcohol, and the like. Examples of the aprotic solvent include nitriles such as R-CN (where R is a linear, branched, or cyclic C2 to C20 hydrocarbon group including a double bond, an aromatic ring, or an ether bond), amides such as dimethylformamide, dioxolans such such as 1,3-dioxolane, sulfolans, or the like.
    [0044] [0044] A single non-aqueous organic solvent can be used, or a mixture of solvents can be used. When a mixture of organic solvents is used, the mixing ratio can be controlled according to the desired performance of the battery.
    [0045] [0045] The carbonate-based solvent can be prepared by mixing a cyclic carbonate and a linear carbonate. Cyclic carbonate and linear carbonate can be mixed together in a volume ratio of about 1: 1 to about 1: 9. Within this range, electrolyte performance can be improved.
    [0046] [0046] In some embodiments of the present invention, the non-aqueous organic electrolyte may include a mixture of a carbonate-based solvent with an aromatic hydrocarbon-based solvent. Carbonate-based and aromatic hydrocarbon-based solvents can be mixed together in a volume ratio ranging from about 1: 1 to about 30: 1. The organic solvent based on aromatic hydrocarbon can be represented by the following Chemical Formula 2.
    [0047] [0047] In Chemical Formula 2, R 1 to R 6 are all independently hydrogen, halogen, an alkyl group C 1 to C 10, an haloalkyl group C 1 to C 10, or a combination thereof.
    [0048] [0048] The aromatic hydrocarbon-based organic solvent may include benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene , chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene , 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4-triiodobenzene, toluene, fluorotoluene, 1,2-difluorotoluene, 1,3-difluorotoluene, 1,4-difluorotoluene, 1,2,3 - trifluorotoluene, 1,2,4-trifluorotoluene, chlorotoluene, 1,2-dichlorotoluene, 1,3-dichlorotoluene, 1,4-dichlorotoluene, 1,2,3-trichlorotoluene, 1,2,4-trichlorotoluene, iodotoluene, 1 , 2-diiodotoluene, 1,3-diiodotoluene, 1,4-diiodotoluene, 1,2,3-triiodotoluene, 1,2,4-triiodotoluene, xylene, or a combination thereof.
    [0049] [0049] As an additive to improve the life cycle, the non-aqueous electrolyte can also include vinylene carbonate, a compound based on ethylene carbonate represented by the following Chemical Formula 3, or a combination thereof.
    [0050] [0050] In Chemical Formula 3, R 7 and R 8 are all independently selected from hydrogen, heavy hydrogen, halogen, a cyano group (CN), a nitro group (NO2), or a fluoroalkyl group C1 to C5, provided that at least minus one of R7 and R 8 is not hydrogen or heavy hydrogen. Specifically, at least one of R 7 and R 8 is selected from halogen, a cyano group (CN), a nitro group (NO2), or a fluoroalkyl group C1 to C5. Examples of the ethylene carbonate-based compound include ethylene difluoro carbonate, ethylene chlorocarbonate, ethylene dichlorocarbonate, ethylene bromocarbonate, ethylene dibromocarbonate, ethylene nitrocarbonate, ethylene cyanocarbonate, ethylene fluorocarbonate, and the like. The amount of vinylene carbonate or ethylene carbonate-based compound used to improve the life cycle can be adjusted within an appropriate range.
    [0051] [0051] Lithium salts dissolved in an organic solvent, provide lithium ions in the battery, allow basic operation of the rechargeable lithium battery, and improve the transport of lithium ion between positive and negative electrodes. Examples of the lithium salt include electrolytic support salts, such as LiBF 4 , LiBF 4 , LiSbF 6 , LíAsF 6 , LiC 4 F 9 SO 3 , LÍC1O 4 , LiAIO 2 , LiAlCl 4 , LiN (CxF 2 x + 1 SO 2 ) (CyF 2 y + 1 SO 2 ), (where x and y are natural numbers), LiCl, Lil, LiB (C 2 O 4 ) 2 (lithium bis (oxalate) borate, LiBOB), or a combination thereof.
    [0052] [0052] The lithium salt can be used in a concentration ranging from about 0.1 M to about 2.0 M. When the lithium salt is included in this concentration range, the electrolyte can have good performance and mobility of lithium ion due to ideal electrolyte conductivity and viscosity.
    [0053] [0053] The separator 113 can include any material commonly used in conventional lithium batteries, as long as it separates the negative electrode 112 from the positive electrode 114 and provides a transport passage for lithium ions. In other words, the separator may have low resistance to ion transport and good electrolyte impregnation. For example, the separator can be selected from fiberglass, polyester, TEFLON (tetrafluoroethylene), polyethylene, polypropylene, polytetrafluoroethylene (PTFE), or a combination thereof. The separator can be a non-woven cloth or a woven cloth. For example, for a lithium ion battery, a polymer separator based on poholefin such as polyethylene, polypropylene or the like can be used. In order to guarantee thermal resistance or mechanical resistance of the lithium ion battery, a coated separator including a ceramic component or a polymeric material can be used. The separator can have a single layer or multiple layers.
    [0054] [0054] According to embodiments of the present invention, the rechargeable lithium battery can further include 1,3-propane sultone (PS), which has been conventionally used to increase durability in thermal impact, as well as the compound represented by the Formula Chemistry 1. According to an embodiment of the present invention, the rechargeable lithium battery including the compound represented by Chemical Formula 1 has notably increased durability in thermal impact due to the inclusion of the compound, and thus may include little or no 1.3 -sultone propane (PS) (which was conventionally used to improve durability in thermal impact, but can cause cancer).
    [0055] [0055] The following examples further illustrate the present invention. These examples are presented for illustrative purposes only, and should in no way be construed to limit the scope of the present invention. Examples 1 to 9: Manufacture of rechargeable lithium battery cell
    [0056] [0056] Rechargeable lithium battery cells according to Examples 1 to 9 were manufactured using LiMnO 2 as a positive electrode, graphite as a negative electrode, and an electrolyte solution having a mixture of ethylene carbonate (EC), carbonate ethyl methyl (EMC), and diethyl carbonate (DEC) in a volume ratio of 3: 5: 2 as a solvent and the composition shown in Table 1 below. The electrolyte was prepared by mixing the solvent and then dissolving 0.95 M LiPF 6 in the mixed solvent, and then adding 6 parts by weight of FEC (ethylene fluorocarbonate), 0.5 parts by weight of VEC (ethylene vinyl carbonate), and 0.2 parts by weight of LiBF 4 as electrolyte additives to it based on 100 parts by weight of the electrolyte. Also, SN (succinonitrile), PS (1,3-propane sultone), 3-MSPN (3-methanesulfonylpropionitrile), and / or 1,3,6-HTCN (1,3,6-hexane tri-cyanide) were respectively added (as indicated in table 1) in an amount of 0 to 3 parts by weight.
    [0057] [0057] The rechargeable lithium battery cells according to Examples 1 and 4 to 9 have been tested for thermal impact in order to compare the thermal impact characteristics of batteries including electrolytes with different types of additives. The results are provided in Table 2 below. The thermal impact test was performed by repeatedly heating and cooling (30 times) rechargeable lithium battery cells from 80 ° C to -40 ° C for one hour to apply voltage. Then, the rechargeable lithium battery cells were allowed to stand at room temperature (after applying thermal impact voltage) and then measured for the increased thickness rate in relation to an initial thickness (ΔT Ini. (%)), A rate increased thickness in relation to a maximum increased thickness (ΔT Max. (%)), increased thickness (mm) in relation to the maximum increased thickness (T Max. (mm)), an increased thickness rate in relation to a thickness (ΔT Abs. (%)), and retention of capacity and recovery capacity.
    [0058] [0058] The capacity retention (%) of the rechargeable lithium battery cells was calculated by measuring the nominal capacity before the test, discharge capacity after the test (charging the rechargeable lithium batteries by the same method), and calculating the “discharge capacity / nominal capacity X 100”.
    [0059] [0059] The recovery capacity (%) of rechargeable lithium battery cells was assessed by performing calculated charge and discharge and calculating “discharge capacity / nominal capacity X 100” after measuring capacity retention. The results are provided in Table 2 below.
    [0060] [0060] As shown in Table 2, the rechargeable lithium battery cell including 1,3,6-HTCN (1,3,6-hexane tri-cyanide) represented by Chemical Formula 1 according to Examples 7 to 9 had improved results (including the increased thickness rate in relation to an initial thickness (ΔT Ini. (%)), the increased thickness rate in relation to the maximum increased thickness (ΔT Max. (%)), the increased thickness (mm ) in relation to the maximum increased thickness (T Max. (mm)), the increased thickness rate in relation to a desired thickness (ΔT Abs. (%)), and the retention and recovery rate after thermal impact) compared to the cell including no BMSE (Bismethanesulfonylethane), 3-MSPN (3-methanesulfonylpropionitrile), or 1,3,6-HTCN according to Example 1 and Examples 4 to 6.
    [0061] [0061] Consequently, battery cells including the 1,3,6-HTCN compound represented by Formula Chemical 1 exhibited improved thermal impact characteristics. Experimental Example 2: Characteristic comparison of thermal impact using similar compound
    [0062] [0062] Succinonitrile (SN, C 2 H 4 (CN) 2 ) and adiponitrile (AN, (CH 2 ) 4 (CN) 2 ) have been conventionally used as additives for rechargeable lithium batteries, and have similar structures to HTCN (tricarbonate hexane), which is a compound that can be represented by Chemical Formula 1. In order to predict surface stabilization effects, side reaction suppression effects, and metal ion bond strength of a positive electrode, the energies bond of coordination of succinonitrile (SN, C 2 H 4 (CN) 2 ), adiponitrile (AN, (CH 2 ) 4 (CN) 2 ) and 1,3,6- HTCN (hexane tricarbonate) between the positive electrode surface (LCO) and an active electrode material was quantum and chemically calculated using functional density theory (DFT) using a PAW method (increased wave projector) and a PBE function (Perdew Burke Emzerhof). As a result, 1,3,6-HTCN (a compound that can be represented by Chemical Formula 1) turned out to be bound to the positive electrode (LCO) surface with about 3.9 and 7.3 kcal / mol strength higher binding than conventional additives, succinonitrile (SN, C 2 H 4 (CN) 2 ) and adiponitrile (AN, (CH 2 ) 4 (CN) 2 ), respectively. The results are provided in table 3.
    [0063] [0063] In addition, the 1,3,6-HTCN complex compound formation energies were calculated with respect to various metal ions, which exist as free ions (PBE0 / 6 - 311 + g (d, p)). These calculations showed that 1,3,6-HTCN was strongly bound with ions such as Co 3+ , Ni 2+ , Fe 2+ , Mn 4+ , Cu + , and the like, and suppress short circuits caused by extraction due to metallic impurities in a battery cell on the negative electrode surface, such as SN or AN. The binding energy with metal ions is provided in Table 4 below.
    [0064] [0064] Without being linked with a specific theory, it is believed that differences in binding energies are caused by the fact that the compound of Formula Chemical 1 (having 3 to 9 functional groups CN and having k, 1, in, that are different from each other and are independently whole numbers from 0 to 20) have an asymmetric structure, which allows the compound to form a stronger coordination link with the metal ion on the surface of the active material or other metal ions in the battery than the SN or AN compounds, which have symmetrical structures.
    [0065] [0065] Referring to FIGs. 3 and 4, the compound represented by Chemical Formula 1 (1,3,6-HTCN) according to embodiments of the present invention has a stronger bond with the active material on the electrode surface or metal ions in a battery cell than conventional compounds having symmetrical structures, such as SN or AN. In order to confirm this effect, the following battery cells according to Examples 10 to 16 were additionally manufactured. Examples 10 to 16: Manufacture of rechargeable lithium battery cells
    [0066] [0066] Rechargeable lithium battery cells according to Examples 10 to 16 were manufactured using LiMnO 2 as a positive electrode, graphite as a negative electrode, and an electrolyte solution prepared by mixing ethylene carbonate (EC), carbonate ethyl methyl (EMC), and diethyl carbonate (DEC) in a volume ratio of 3: 5: 2 as a solvent and dissolving 0.95 M of LiPF 6 in it, and then adding 6 parts by weight of FEC (ethylene fluorocarbonate), 0.5 parts by weight of VEC (ethylene vinyl carbonate), and 0.2 parts by weight of LiBF 4 as electrolyte additives based on 100 parts by weight of the electrolyte. Also, SN (succinonitrile) and PS (1,3-propane sultone) were added in an amount of 0 to 4 parts by weight according to Table 5 below. Additionally, 1,3,6-HTCN (1,3,6-hexane tri-cyanide) in an amount of 0 to 3 parts by weight, or 1,2,3-PTCN (1,2,3-propane tricarbonitrile ), or 1,3,5-PTCN (1,3,5-penta tri-cyanide) in an amount of 0 to 1 part by weight was added according to Table 5 below. Both 1,2,3-PTCN and 1,3,5-PTCN are similar to 1,3,6-HTCN in that they are all hydrocarbon compounds having three CN functional groups. However, 1,2,3-PTCN and 1,3,5-PTCN have symmetrical molecular structures, as opposed to 1,3,6-HTCN.
    [0067] [0067] The rechargeable lithium battery cell according to Example 10 was used as a control group since it included neither 1,3,6-HTCN nor a compound having a symmetrical structure. The compositions of the electrolyte additives according to the Examples are provided in Table 5 below, and the rechargeable lithium batteries including the additives were tested to ascertain the thermal impact characteristics as in Experimental Example 1. The results are given in Table 6. In Table 5 below, the quantities listed for each additive or solvent are reported as parts by weight.
    [0068] [0068] As shown in Table 6, when 1,3,6-HTCN (which can be represented by Chemical Formula 1) was used as an additive (Examples 11 to 14) the batteries had improved effects in terms of increased thickness rate in relation to the initial thickness, increased thickness ratio in relation to the maximum increased thickness, capacity retention, and recoverability after thermal impact when compared to the Examples not including any 1,3,6-HTCN (Example 10) and Examples including 1,2,3-PTCN or 1,3,5-PTCN having similar but symmetrical structures (Examples 15 and 16). Experimental Example 3: Coordination bonding energies between compounds on an electrode surface and active electrode material
    [0069] [0069] The coordinating binding energies of 1,2,3-PTCN, 1,3,5-PTCN, 1,3,6-HTCN, and 1,2,6-HTCN among the compounds on the positive electrode surface (LiMnO 2 ) and the active electrode material were quantum and chemically calculated using a functional density theory (DFT) using a PAW method (increased wave projector) and a PBE function in order to predict the stabilization effect of positive electrode surface, the effects of suppression of side reactions, and the binding forces with metal ions. The results are provided in Table 7 below. Here, the results of the SN compound are also provided for comparison.
    [0070] [0070] As shown in table 7, 1,3,6-HTCN and 1,2,6-HTCN (compounds that can be represented by Chemical Formula 1) are bonded to the surface of the positive electrode (LiMnO 2 ) with bond strength higher than 1,2,3-PTCN or 1,3,5-PTCN, which have similar but symmetrical structures.
    [0071] [0071] Furthermore, FIG. 5 is a schematic showing the ways in which the compounds bond with the surface of the electrode material. As shown in FIG. 5, the compounds (1,3,6-HTCN and 1,2,6-HTCN) represented by Chemical Formula 1 according to embodiments of the present invention are more stably bonded on the surface of the positive electrode (LCO) than 1 , 2,3-FTCN or 1,3,5-PTCN, which have similar but symmetrical structures.
    [0072] [0072] Rechargeable lithium battery cells including the compound represented by Formula Chemical 1 have notably improved thermal impact durability since the compound represented by Formula Chemical 1 is bonded with the electrode surface material and suppresses the generation of gas on the surface positive electrode. In addition, the battery cells have coordination links of the compound represented by Chemical Formula 1 with metal ions, thus preventing short circuits due to the extraction of metal ions on the surface of the negative electrode. Consequently, rechargeable lithium batteries including the compound represented by Chemical Formula 1 can replace rechargeable lithium batteries including PS (a conventional additive used to improve durability on thermal impact, but which possibly causes cancer).
    [0073] [0073] Although the present invention has been illustrated and described in relation to certain exemplary embodiments, it should be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included in the spirit and scope of the appended claims.
    权利要求:
    Claims (7)
    [0001]
    Rechargeable lithium battery (100; 1), comprising: a positive electrode (114; 3); a negative electrode (112; 2); and an electrolyte composition; the battery (100; 1) being characterized by the fact that it additionally comprises a compound represented by Chemical Formula 1 in at least one of the positive electrode (114; 3), the negative electrode (112; 2) or the electrolyte:
    [0002]
    Rechargeable lithium battery (100; 1) according to claim 1, characterized by the fact that k is 0, and 1 and m are independently whole numbers from 1 to 5.
    [0003]
    Rechargeable lithium battery (100; 1) according to claim 1, characterized by the fact that the compound represented by Chemical Formula 1 is 1,3,6-hexane tri-cyanide, or 1,2 tri-cyanide, 6- hexane.
    [0004]
    Electrode composition for the rechargeable lithium battery (100; 1) as defined in any one of claims 1 to 3, the electrode composition characterized by the fact that it comprises: an active electrode material; and a compound represented by Chemical Formula 1:
    [0005]
    Electrode composition according to claim 4, characterized by the fact that the active electrode material is a positive active material.
    [0006]
    Electrode composition according to claim 4, characterized by the fact that the active electrode material is a negative active material.
    [0007]
    Electrolyte composition for the rechargeable lithium battery (100; 1) as defined in any one of claims 1 to 3, the electrolyte composition characterized by the fact that it comprises: a solvent; a lithium salt; and a compound represented by Chemical Formula 1: on what: each of k, 1 in and is independently an integer from 0 to 7, and k, 1 in are different from each other, with which the compound of Formula 1 has an asymmetric structure, and n is an integer from 1 to 1, and wherein an amount of the compound represented by Chemical Formula 1 is 0.1 to 10% by weight based on a total weight of the electrode composition.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR102013018778B1|2020-06-30|rechargeable lithium battery, and electrode and electrolyte compositions for the rechargeable lithium battery
    US10916806B2|2021-02-09|Electrolyte for lithium secondary battery, and lithium secondary battery comprising electrolyte
    JP2008130544A|2008-06-05|Electrolyte for lithium secondary battery, and lithium secondary battery containing the same
    JP2013235830A|2013-11-21|Electrolyte for lithium secondary battery, and lithium secondary battery including the same
    EP2824750B1|2019-01-30|Silicon-containing compound used in electrolytes for lithium secondary batteries
    JP6335543B2|2018-05-30|ELECTROLYTE SOLUTION FOR LITHIUM SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY CONTAINING THE SAME
    KR102130028B1|2020-07-03|Rechargeable lithium battery
    US11038203B2|2021-06-15|Lithium secondary battery
    JP6072479B2|2017-02-01|Lithium secondary battery electrolyte and lithium battery employing the same
    US10985404B2|2021-04-20|Electrolyte for lithium secondary battery, and lithium secondary battery comprising electrolyte
    US11056719B2|2021-07-06|Lithium secondary battery comprising electrolyte
    US9799924B2|2017-10-24|Electrolyte solution for secondary lithium battery and secondary lithium battery using the same
    US11056720B2|2021-07-06|Lithium secondary battery comprising electrolyte
    US11038204B2|2021-06-15|Lithium secondary battery
    US20200153045A1|2020-05-14|Electrolyte for lithium secondary battery, and lithium secondary battery comprising same
    KR20110036444A|2011-04-07|Rechargeable lithium battery
    KR101837036B1|2018-03-09|Electrolyte Solution for Lithium Secondary Battery and Lithium Secondary Battery Using the same
    JP2014049443A|2014-03-17|Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery including the same
    KR102152306B1|2020-09-04|Electrolyte for rechargeable lithium battery and rechargeable lithium battery
    US11050129B2|2021-06-29|Electrode for lithium secondary battery and lithium secondary battery comprising same
    KR101702981B1|2017-02-06|Electrolyte and rechargeable lithium battery including the same
    US9935334B2|2018-04-03|Electrolyte and rechargeable lithium battery including same
    US20210005932A1|2021-01-07|Lithium secondary battery comprising electrolyte
    US20210083295A1|2021-03-18|Rechargeable lithium battery
    CN112542608A|2021-03-23|Rechargeable lithium battery and method of manufacturing the same
    同族专利:
    公开号 | 公开日
    EP2706600B1|2015-04-01|
    EP2706600A1|2014-03-12|
    BR102013018778A2|2017-12-12|
    JP2014053307A|2014-03-20|
    US20140072865A1|2014-03-13|
    KR101765190B1|2017-08-04|
    KR20140032918A|2014-03-17|
    US9819057B2|2017-11-14|
    CN103682416A|2014-03-26|
    CN103682416B|2018-02-09|
    JP6312391B2|2018-04-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPH0343351B2|1986-10-30|1991-07-02|Asahi Chemical Ind|
    WO1997035332A1|1996-03-20|1997-09-25|Ecole Polytechnique Federale De Lausanne|Electrochemical device and electrolyte therefor|
    CA2215849A1|1997-09-11|1999-03-11|Dany Brouillette|New solvent and electrolytic composition with high conductivity and wide stability range|
    CA2283670C|1998-02-03|2011-06-07|Acep Inc.|Materials useful as electrolytic solutes|
    KR100588288B1|2004-02-16|2006-06-09|주식회사 엘지화학|Electrode for lithium secondary battery|
    US20050194562A1|2004-02-23|2005-09-08|Lavoie Raymond L.Jr.|Polishing compositions for controlling metal interconnect removal rate in semiconductor wafers|
    JP2007158203A|2005-12-08|2007-06-21|Nichicon Corp|Electrolytic capacitor|
    KR100941299B1|2006-07-07|2010-02-11|주식회사 엘지화학|Additive having cyano group for non-aqueous electrolyte and electrochemical device using the same|
    JP4936440B2|2006-10-26|2012-05-23|日立マクセルエナジー株式会社|Non-aqueous secondary battery|
    KR20160011227A|2006-12-06|2016-01-29|미쓰비시 가가꾸 가부시키가이샤|Nonaqueous electrolyte solution and nonaqueous electrolyte secondary battery|
    KR100865402B1|2007-06-12|2008-10-24|삼성에스디아이 주식회사|Nonaqueous electrolytes for rechargeable battery and rechargeable battery using the same|
    JP5593592B2|2007-06-28|2014-09-24|三菱化学株式会社|Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery using the same|
    JP5217400B2|2007-06-28|2013-06-19|三菱化学株式会社|Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery using the same|
    GB2457664A|2008-02-19|2009-08-26|Science Technology Res Partner|Electrolyte composition for a dye sensitized solar cell|
    CN101521297A|2008-02-26|2009-09-02|三洋电机株式会社|Non-aqueous electrolyte secondary battery|
    JP2009231261A|2008-02-26|2009-10-08|Sanyo Electric Co Ltd|Nonaqueous electrolyte secondary battery|
    JP2010073367A|2008-09-16|2010-04-02|Sony Corp|Nonaqueous electrolyte, and nonaqueous electrolyte battery|
    JP5619412B2|2009-09-04|2014-11-05|三洋電機株式会社|Non-aqueous electrolyte secondary battery and method for producing non-aqueous electrolyte secondary battery|
    JP2014523841A|2011-06-07|2014-09-18|ファーストキャップ・システムズ・コーポレイション|Energy storage medium for ultracapacitors|
    US20130316252A1|2012-05-22|2013-11-28|Lg Chem, Ltd.|Non-Aqueous Electrolyte Solution For Lithium Secondary Battery And Lithium Secondary Battery Comprising The Same|US9979049B2|2013-12-09|2018-05-22|Sk Innovation Co., Ltd.|Electrolyte for lithium secondary battery and lithium secondary battery comprising same|
    CN104766995B|2015-03-31|2017-03-15|宁德时代新能源科技股份有限公司|A kind of electrolysis additive and its application in lithium ion battery|
    JP6830904B2|2015-04-20|2021-02-17|アンテオ テクノロジーズ プロプライエタリー リミテッドＡｎｔｅｏ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｐｔｙ Ｌｔｄ|Composition|
    KR20170028143A|2015-09-03|2017-03-13|삼성에스디아이 주식회사|Electrolyte for rechargeable lithium battery and rechargeable lithium battery|
    CN105481719B|2015-12-24|2018-02-02|天津广顺化学科技有限公司|The preparation method of the nitrile of 1,3,4,6-hexane four|
    KR102294961B1|2016-04-04|2021-08-26|삼성에스디아이 주식회사|Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same|
    CN108232300A|2018-01-05|2018-06-29|宁德新能源科技有限公司|A kind of lithium ion battery and its electrolyte|
    CN112002942A|2018-09-21|2020-11-27|宁德新能源科技有限公司|Electrolyte and electrochemical device containing same|
    CN109301326B|2018-09-21|2020-11-27|宁德新能源科技有限公司|Electrolyte and electrochemical device|
    CN111740161A|2018-09-21|2020-10-02|宁德新能源科技有限公司|Electrolyte and electrochemical device comprising the same|
    EP3951989A1|2019-11-07|2022-02-09|Lg Energy Solution, Ltd.|Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same|
    US20210242503A1|2020-01-31|2021-08-05|Ascend Performance Materials Operations Llc|Electrolyte solutions|
    KR20210106817A|2020-02-21|2021-08-31|주식회사 엘지화학|Screening method of the electrolyte additive, electrolyte additive for secondary battery, and non-aqueous electrolyte solution for secondary battery comprising the same|
    CN111916824B|2020-06-30|2021-11-09|珠海冠宇电池股份有限公司|Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same|
    法律状态:
    2017-12-12| B03A| Publication of an application: publication of a patent application or of a certificate of addition of invention|
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2018-03-20| B06I| Technical and formal requirements: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-04-22| B09A| Decision: intention to grant|
    2020-06-30| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/07/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261698311P| true| 2012-09-07|2012-09-07|
    US61/698311|2012-09-07|
    US13/830,119|US9819057B2|2012-09-07|2013-03-14|Rechargeable lithium battery|
    US13/830119|2013-03-14|
    [返回顶部]