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    • 专利摘要:
    Electrodeposition involving an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and/or film surface. For electrodeposition of a first conductive material (C1) on a substrate from one or more reactants in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second conductive material (C2), wherein cations of C2 have an effective electrochemical reduction potential in the solution lower than that of the reactants.
    公开号:AU2012369141A1
    申请号:U2012369141
    申请日:2012-12-18
    公开日:2014-06-19
    发明作者:Xilin Chen；Fei Ding；Gordon L. Graff；Yuyan SHAO；Wu Xu；Jiguang Zhang
    申请人:Battelle Memorial Institute Inc；
    IPC主号:C25D5-10
    专利说明:
    WO 2013/119322 PCT/US2012/070288 Methods and Electrolytes for Electrodeposition of Smooth Films Priority j00011 This invention claims priority to U.S. Patent No. 13/367,508, filed. February 7, 201.2, entitled Dendrite-inhibiting Salts in Eectrolytes ofinergy Storage Devices and US. PatentN. N 3/419527, filed Junie 13 2012, entitled MI-lethodS and Electrofvresf.>,r Statement Regarding Federally Sponsored Research or Development [0002] This invention was made with Government support under Contract i-ACO576R LOI830 awarded by the U.S. Department of Energy. 'iThe Govennent has certain rights in this invention. Cross-Reference to Related Applications 100031 This invention claims priority from, and is a continuation in part of, currently pending U. S. Patent Application No. 13/367,508, filed February 7, 2012, incorporated herein by reference. Background [0004] Eliectrodeposition is widely used to coat a functional material having a desired property onto a surface that otherwise lacks that property. During electrodeposition, electrically charged reactants in an electrolyte solution diffuse, or are moved bv an electric leid, to cover the surface of an electrode. For example, the electrical current can reduce I1 WO 2013/119322 PCT/US2012/070288 reactant nations to Vield a deposit on an anode, Or, anions of reactants in the electrolyte solution can diffuse, or be moved by the electric field, to cover the surface of a cathode, where the reactant anions are oxidized to torms a deposit on, the electrode. 10005 1 Eiectrodeposition has been successfully utilized in the fields of abrasion and wear resistance, corrosion protection, ub ricity, aesthetic qualities, etc. It also occurs in the operation of certain energy storage devices. For example, in the charge process of a metal battery or metal-ion battery, metal ions in the electrolyte move from the cathode and are deposited on the anode Some organic compounds with unsaturated carbon-carbon double or triple bonds are used as additives in non-aqueous electrolytes and are electrochemically reduced and deposited at the anode surface or oxidized and deposited at the cathode surface to forn solid electrolyte interphase layers as protection films on both anode and cathode of lithium batteries. Some other organic compounds with conjugated bonds in the molecules are electrochemically oxidized and deposited at the cathode surface to forn electric conductive polymers as organic cathode materials for energy storage devices. 100061 In most instances, the ideal is a smooth electrodeposited coating. For example, a smoothly plated film can enhance the lifetime of a film used for decoration, wear resistance, corrosion protection., and lubrication. A smoothly plated film is also required for energy storage devices, especially for secondary devices. Rough films and/or dendrites generated on electrode surfaces during the charge/discharge processes of these enerv storage devices can lead to the dangerous situations, short-circuits, reduced capacities, and/or shortened lietimues. 100071 Roughness and/or dendrites can be caused by several reasons, including the uneven distribution of electric current density across the surface of the electrodeposition 2 WO 2013/119322 PCT/US2012/070288 substrate (e.g.. anode) and the uneven reactivity of electrodenosited material and/or substrate to electrolyte solvents, reactants, and salts. These effects can be compounded in the particular case of repeated charging-discharging cycles in energy storage devices. Therefore, a need for improved electrolytes and methods for electrodeposition are needed to enhance the smoothness of the resultant film. Summary 100081 This document describes methods and electrolytes for electrodeposition that result in self-healing, instead of self-amplification, of initial protubernt tips, which are unavoidable electrodeposition and which give rise to roughness and/or dendrite formation. For electrodeposition of a first conductive material (Cl) on a substrate from one or more reactants in an electrolyte solution, enbodiments of the electrolyte solution described herein are characterized by a soluble, surface-smoothing additive comprising cations of a second conductive material (C2), wherein cations of C2 have an effective electrochemical reduction potential (ERP) in the solution lower than that of the reactants. [0009] As used herein, cations, in the context of C , C2, and/or reactants, refer to atoms or molecules having a net positive electrical charge. in but one example, the total number of electrons in the atom or molecule can be less than the total number of protons, giving the atom or molecule a net positive electrical charge, The cations are not necessarily cautions of metals, but can also be non-metallic cations. At least one example of a non-metallic cation is ammonium. Cations are not limited to the -1 oxidation state in any particular instance. In some descriptions herein, a cation can be generally represented as X% which refers generally to any oxidation state, not just +1.
    WO 2013/119322 PCT/US2012/070288 [0010] In another example, the reactants mTght not technically be cations but are positive charged species such as conductive monomers/polymers. Duringthe electrodeposition of a metal cation, the cation gets the electron at the anode and is reduced to metal. When morning a conductive polymer via electrodeposition, it is the conjugated monomer, which can be neutral but with double or triple bonds, that gets the electrons. The conjugatedi monomer re-arranges the double or triple bonds among the same molecular structure and forms new bonds among different molecules. The formed polymer is either neutral or positively charged when protons are incorporated onto the polymer moxety [0011] In one embodiment, CI is a metallic material and the reactants comprise cautions of C1, Examples of suitable metallic materials include, but are not limited to,. elemental metals or alloys contain Li, NaK, Rbr, B Ba A, AlGa,In, l, Ge, Sn, Pb, As., Sb, Bi, Se, Te, Bi, Po, Sc, Ti. V, Cr., Mn. Fe, Co, Ni, Cu. Zn, Y, Zr, No, Mo, Tc, Ru, Rh, Pd, Ag, Cd, W. Pt. Au, and/or ig. Preferably, C is an elemental metal material comprising Li, Zn, Na, Mg Al., Sn, Ti, Fe, Ni, Cu, Zn, Ag, Pt, or Au. [0012j Alternatively, CI can comprise an electronic conductive polymer. In such instances, the reactants can comprise monomers of the polymer. The monomers can be conjugated monomers that are reduced at the anode during deposition. Examples of polymers can include, but are not limited to, polyanaline, polypyrrole, poilythiophene, poiy(3,4-ethylenedioxythiophene), Monomers of these polymers can include. but are not limited to, analine. nvrrole, thiophen. 3,4-ethylenedioxythiophene, respectively. {0013] in another embodiment, the cations of C2 are metal cations. Examples of metals for cations of C2 include, but are not limited to, Li, Cs, Rb, K, Ba, La, Sr, Ca, Ra, Zr, 'Fe, B, Bi, Ta, Ca, Eu, S, Se, Nb, Na, Mg, Cu. Al, Fe, Zn, Ni, Ti, Sn, S-, Mn, V, Ta, Cr, Au, Ge, 4 WO 2013/119322 PCT/US2012/070288 Co, As, Ag, Mo, Si, W, Ru, I, Fe, Br, Re. Bi, Pt. and/or Pd. in preferred embodiments, nations of C-2 are cations of Cs, Rb. K, Ba, Sr, Ca, Li. [0014j A cation of (2 might have a standard reduction potential that is greater than that of the reactants. In such instances, some embodiments of the electrolyteshave an activity of C2 cautions such that the effective ERP of the C2 cations is lower than that of the reactants (Cl). Because activity is directly proportional to the concentration and activity coefficient, which depend on the mobility and solvation of the cation in the given electrolyte, a lower activiy can be a result of low concentration, low activity coefficient of the cations, or both since the activity is the product of the activity coefficient and concentration, The relationship between effective ERP and activity is described in part by the Nernst equaton and is explained in further detail elsewhere herein. In a particular enbodiment, the concetration of C2 cationsis less than, or equal to, 30% of that of the reactants. In another, the concentration of C92 nations is less than, or equal to, 10% of that of the reactants. In yet another, the concentration of C2 cations is less than, or equal to, 5% of that of the reactants [0015] The surface-smnoothing additive can comprise an anion that includes, but is not iited to, P1<, AsF], BIF, N(SO2CF, N(SO+F72, CF 3 SO, ClO, , Cl', OH^, NOt, SO, and combinations thereof. Preferably, the anion comprises PFG. [0016j In one embodiment, the substrate is an electrode. For example, the substrate on which electrodeposition occurs can be an electrode in an energy storage device, In particular instances, the electrode can comprise lithium, carbon, magnesium, and/or sodium. As used herein, electrode is not restricted to a complete structure having both an active material and a current collector. For example, an electrode can initially encompass a current collector on which active material is eventually deposited to form an anode. Aitenatively, an electrode WO 2013/119322 PCT/US2012/070288 can start out as an active material pasted on a current collector. After initial cycling, the active material can be driven into the current collector to yield what is traditionally referred to as an electrode.. [00171 Preferably, the cautions of C2 are not chemically or electrochemically reactive with respect to C I or the reactants. Accordingly, the surtee-smoothing additive is not necessarily consumed during electrodeposition. 100181 The electrolyte also comprises a solvent. Examples of solvents can include, but are not limited to, water or a non-aqueous polar organic substance that dissolves the solutes at room temperature. Blends of more than one solvent can be used, When water or a protie organic substance is used as the solvent, Cl is not a metal that reacts with water or the protic organic substance. Generally, organic solvents can include, but are not limited to., alcohols. ethers. aldehydes, ketones, carbonates, carboxylates., lactones, phosphates, nitriles, sulfones, amides, five or six member heterocyclic ring compounds, and organic compounds having at ieastone CJC4 group connected through an oxygen atom to a carbon. Laciones may be mnethlated, ethvlated and/or propylated. Other organic solvents can include inethanol, ethanol, acetone. sulilane, dimethyl sulfone, ethyl methyl sulftone, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, tetrahydrofuran, 2-methyl tetrahvdrofuran, 1,3-dioxolane, 1,4-dioxane, ,i x n 2-diethoxyethane, I,2-dibutoxyethane, acetonitrile, dimethylformamide, methyl formate, ethyl format propyl iformate, butyl formate. methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propel propionate, buty] propionate, methyl butyrate, ethyl butyrate propyl butyrate, butyl butyrate, gamna-butyroIactone, 2-methy!-gamma-buactonectone, 3-methyl-ganmma 6 WO 2013/119322 PCT/US2012/070288 butyrolactone 4-meth yl-gamrma-butyrol actone, delta-valerolactone, trimethyl phosphate, triethyl phosphate, tris(2,2,2-trifluoroethyl) phosphate, tripropyl phosphate, triisopropyl phosphate, tributyi phosphate, trihexy phosphate, triphenyl phosphate, and combinations thereot. Still other non-aqueous solvents can be used so long as they are capable of dissolving the solute salts. 10019] Methods for improving surface smoothness during electrodeposition of Cl on a substrate surface can comprise providing an electrolyte solution comprising reactants from which CA is deposited and a soluble, surface-smoothing additive comprising cations of a second conductive material (C2) and applying an electrical potential thereby reducing the reactants and forming CI on the substrate surface. The cations of C2 have an effective electrochenical reduction potential in the solution lower than that of the reactants. In preferred embodiments, the methods further comprise accumulating cations of C2 at protrusions on the substrate surface, thereby forming an electrostatically shielded region near each protrusion. The electrostatically shielded region can temporarily repel reactants, thus reducing the local effective current density and slowing deposition at the protrusion while enhancing deposition in regions away from the protrusions. In this way, the growth and/or amplification of the protrusions are suppressed and the surface heals to yield a relatively smoother surface. 100201 in one embodiment., the method is applied to electrodeposition of ithium on a substrate surface. Lithiun is an effective example because Li> ions have the lowest standard BRP among metals (at a concentration ofi mol/, a temperature of 298.15 K (25 C and a partial pressure of 101,325 kPa (absolute) (1 atm, 1.01325 bar) for each gaseous reagent). 7 WO 2013/119322 PCT/US2012/070288 (2 cations, which have standard EPR values that are greater than lithium cations can have activity-dependent effective ERP values that are lower than those of the lithium cations. [00211 According to such embodiments, the method comprises providing an electrolyte solution comprising lithium cations and a soluble, surface-smoothing additive comprising cations of a second conductive material (C2) selected from the group consisting of cesium, rubidium, potassium, strontium, barium, calcium, and combinations thereof. The nations of C2 have a concentration and activity coefficient in solution stch that the effective electrochemical reduction potential of the cautions of C2 is lower thm that of the lithium cautions. The method further comprises applying an electrical potential, thereby reducing the ithiun.m nations and forming lithium on the substrate surface. The method further comprises accumulating caions of C2 at protrusions on the substrate surface, thereby forning an electrostaticalli shielded region near each protrusion and temporarily repelling the lithium nations from the electrostatically shielded regions. In some instances, the electrostatically shielded region has a higher impedance to retard the further deposition of lithium cations. 10022] In particular embodiments. the concentration of (2 cautions is less than, or equal to 30% of that of the lithium cations. in others, the C2 cation concentration is less than, or equal to, 5% of that of the lithium cations. Preferably, the surface-smoothing additive comprises an anion comprising P<I anion. The substrate can be a batten anode that comprises lithium or that comprises carbon, 10023] The purpose of the foregoing abstract is to enable the United States Patent and Trademark Office and the public generally. especially the scientists, engineers, and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical 8 WO 2013/119322 PCT/US2012/070288 disclosure of the application. The abstract is neither intended to define the invention o the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way, [00241 Various advantages and novel features of the present invention are described herein and will become further readily apparent to those skilled in this art from the fol lowing detailed description. In the preceding and following descriptions, the various embodinents, including the preferred embodiments, have been shown and described. included herein is a description of the best mode contemplated for carrying out the invention. As wil! be realized, the invention is capable of modification in various respects without departingzfrom the invention. Accordingly, the drawings and description of the preferred embodiments set forth hereafter are to be regarded as illustrative in nature. and not as restrictive. Description of Drawings [00251 Embodiments of the invention are described below with reference to the following accompanying drawings. [00261 Figs. I A 1F are illustrations depicting an embodiment of electrodeposition using an electrolyte having a surface-smoothing additive. [00271 Figs. 2A - 21) include SEM micrographs of Li films deposited in an electrolyte with or without a surface-smoothing additive according to embodiments of the present invention; (a) No additive; (b) 0.05 MI RbPF(; (c) 0.05 N CsPF6; (d) 0.15 M KPZ 0 . 100281 Figs A - 3B include SEM micrographs of pre-formed dendritic Li film deposited in a control electrolyte for 1 hour and the same film after another 14 hours' Li deposition in the electrolyte with additive (0.05M CsPF), respectively. 9 WO 2013/119322 PCT/US2012/070288 [0029! Figs, 4A - 4F include SEM inicrographs of Li electrodes after repeated deposition/stripping cycles in the control electrolytes (a. b, and c) and with Cs-salt additive (d, e and f [00301 Figs. 5A - 5B include SEM micrographs of Li electrodes after 100 cycles in coin cells of Li Lti9 fi; containing electrolytes without (a) and with (b) 0.05 M Cs' additive. 10031] Figs. 6A - 6F include optical and SEM micrographs of hard carbon electrodes after charging to 300% of the regular capacity in the control electrolyte (a, c, c) and in an electrolyte with. 0.05 M CsPF additive added in the control electrolyte (b, d, 1). Detailed Description 100321 The. following description includes the preferred best mode of one embodiment of the present invention. It will be clear from this description of the invention that the invention is not limited to these illustrated embodiments but that the invention also includes a variety of modifications and embodiments thereto. Therefore the presen t description should be seen as illustrative and not limiting. While the invention is susceptible of various modifications and alternative constructions, it should be understood, that there is no intention to limit the invention to the specific form disclosed, but, on the contrary. the invention is to cover all modifications, alternative constructions, and equivalents failing within the spirit and scope of the invention as defined in the claims. 10033] Figures 1-6 shox a variety of embodiments and aspects of the present invention. Referring first to Figure I, a series of illustrations depict an embodiment of electrodeposition using an electrolyte 104 having a surface-smoothing additive. The additive comprises cations of C2 102. which have an effective ERP lower than that of the reactants 103. Figure 10 WO 2013/119322 PCT/US2012/070288 1 illustrates how an electrostatically shielded region 106 can develop resulting in the self heain of the unavoidable occurrence of surface protrusions 105 that would normally forn During the initial stage of deposition, both the reactants and the nations of C2 are adsorbed on the substrate surface 100 (Figure IA) under an applied voltage (E,) 101 slightly less ihan the reduction potential of the reactant (E,) but larger than the additive reduction potential E,. ), that is, Er >, E..> ,, ). Reactants will be deposited to form C. on the substrate and will unavoidably forn some protuberance tips due to various fluctuations in the system (Figure 1B). A sharp edge or protrusion on the electrode exhibits a stronger electrical field, which will attract more positively charged cations (including both C1 and C2,) Therefore, more nations of C I will be preferentially deposited around the tips rather than on other smooth regions. in conventional electrodeposition, amplification of this behavior will form the surface roughness andior dendrites. However, according to embodiments of the present invention, the adsorbed additive cations (C2') have an effective ERP lower than Ea (Figure IC) and wfil not be deposited (i.e., electrochemically or chemically consumed, reacted,. and/or permanently bound) on the tip. instead, they will be temporarily electrostatically attracted to and accumulated in the vicinity of the tip to form an electrostatic shield (F igure ID). This positively charged shield will repel incoming reactants (e.g, like-charged species) at the protruded region and force them to be deposited in non-protrusion regions. The net effect is that reactants will be preferentially deposited in the smoother regions of the substrate (Figure 1 E) resulting in a smoother overall deposition surface (Figure 1F). This process is persistently occurring and/or repeating during electrodeposition. The self-healing mechanism described herein resulting from embodiments of the present invention appears to I i WO 2013/119322 PCT/US2012/070288 disrupt the conventional roughness and/or dendrite amplification mechanism and leads to the deposition of a smooth film of C1 on the substrate. 10034] The additive cation (C2v) exhibits an effective ERPEless than h'at of the cations (Cl ) of the reactants. In some instances, the standard ERP of the C2 cation will be less than that of the reactants. Surface-smoothing additives comprising such C2 species can be utilized with appropriate reactants with few initations on concentration and activity coeficient However, in some instances, the C2 cation will have a standard ERP that is greater than that of the reactants. The concentration and activity coefficient of the C2 cations can be controlled such that the effective IERP of the C2 cations is lower than that of the reactant nations. For example, if the reactant is a Li* ion, which has the lowest standard ERP ainong metals, then the concentration and activity coefficient of ('2 cations can be controlled such that the effective ERP is lower than that of the lithium cations, 10035 According to the Nenst equation: zF T where R is the universal gas constant (:::8.314 472 J K' mol ) is the absolute temperature (assume T =:25"C in this work), (: is the activity for the relevant species (a/, is for the reductant and axsx is for the oxidant). a ypc where ',' and c, are the activity coefficient and the concentration of species x . F is the Faraday constant (9.648 533 99x 10" C mol z is the number of moles of electrons transferred. Although Li" ion has the lowest standard reduction potential. E (Li*), among all the metals when measured at a standard conditions (I mol/l), a cation (M*) may, have an effective reduction potential lower than 12 WO 2013/119322 PCT/US2012/070288 those of lithium ion (Lit) if N" has an activity a, much lower than that of Li. in the case of ow concentration when the activity coefficient is unity, a can be simplified as concentration c, , then Eq. (i) can be simplified as: 0.05916V , (2) 10036] Table I shows several the reduction potentials for several cations (vs. standard hydrogen electrode (SHE)) at various concentrations assuming that their activity coefficients y, equal one. When the concentration of Cs ', Rb". and K' is 0.01 M in an electrolyte, their efctive ERPs are -3.144 V, -3098 V and -3.049 V, respectively, which are lcss than those of Li at I A concentration (-3.040 V). As a result, in a mixed electrolyte where the additive (Cs% Rbr, and K") concentration is much less than Li concentration, these additives will not be deposited at the lithium deposition potential. In addition to a low concentradtonc, , a Very low activity coefficient 7. (which is strongly affected by the solvation and mobilit of the nations in the given solvent and lithium salt) rnay also reduce the activity of cations and lead to an effective reduction potential lower than that of the lithium ion (Li) as discussed below. Table 1. The effective reduction potential of selected cations vs. SHE * Cs RbK Stand reduction potent a (M 3.04 V 3(026 V ~,980 V -2.93. V ETffective reduction poteAt a 3103 V -3.06V 6 V at 0.05* . - -- -- - - -- - - -- -- - ......... --- -- --.--- -- E effective reduction potent'a - - .~3f144V 31098V 31049 V a. 0.01M* 13 WO 2013/119322 PCT/US2012/070288 *Assumqe the activity coefficient , of species x equals L Surface Smoothing Exhibited in Electrodeposition of Lithium [0037l Enbodiments of the present invention are illustrated well in the electrodeposition of lithium, since lithium ions have the lowest standard ERP among metals, However, the present in venion is not Limited to lithium but is defined by the claims. 100381 The effect of several C2 nations has been examined "or use in surface-smoothing additives in the electrodeposition of lithitum. The cations all have standard ERP values, Ef that are close to that of Li ions, Ihe electrolyite comprised 1 M LiPFf in propylene carbonate. Electrolyte solutions with surface-smoothing additives comqfrisminz 0.05 M RhPE, 0.5 M CsPF, or 0.15 M KPF were compared to a control electrolyte with no additives. CsPF 6 , RbP>F, and Sr(PF>)2 were synthesized by mixing stoichiometric amount of AgPQK and the iodide salts of Cs, Rb, or Sr in a PC solution inside a glove box filled with purified argon where the oxygen and moisture content was less than I ppm. The formed Agl was filtered out from the solution using 0.45 pm syringe filters. The electrolyte preparation and lithium deposition were conducted inside the glove box as well. Lithium films were deposited on copper (Cu) foil substrates (I Wam x 10mm) in different electrolyte solutions at the desired current densities using a SOLARTR)N*> electrochemical Interface. After deposition the electrode was washed wvith DMC to remove the residual electrolyte solvent and salt before the analyses. 10039] Referring to the scanning electron microscope (SEM) micrograph in Fitgure 2A. 'When using the control electrolyte, the electrodeposited film exhibited conventional 14 WO 2013/119322 PCT/US2012/070288 roughness and dendrite growth. The lithium film deposited in the electrolyte with 0.05 M Rb" as the C12 cation exhibits a very fine surface morphology without dendrite formation as shown in Figure 2B, Similarly, for the lithium films deposited with 0.05 M Cs additive, a dramatic change of the lithium morphology with no dendrite formation (see Figure 2C) was obtained compared with the control experiment. Surprisingly, although E,,,, (K-) at 0,15 M is theoretically -0.06 V higher than that of Li' assuming both K and Li have an activity coefflcient of 1 K metal did not deposit at the lithium deposition potential, and alithium film with a mirror-like mnorphology was obtained using K' as in the additive (Figure 2D). This experimental finding suggests that the activity coefficient , for K' ion's in this electrolyte is much less than those of LiV leading to an actual E, (K) lower than E' (Li.). [0040] Generally, the concentration of the surtace-smoothirig additive is preferably high enough that protrusions can be effectively electrostatically shielded considering the effective ERP, the number of available C2 cations, and the mobility of the C2 cations, F'or example, in one embodiment, wherein the C2 cation comprises K', the reactant comprises Li and C-1 comprises ithium metal, the concentration of K is greater than 0.05M. 10041] Referring to Figure 3A, a dendritic lithium film was intentionally deposited on a copper substrate in a control electrolyte for 1 hour, The substrate and film was then transferred into an electrolyte comprising a surface-smoothing additive, 0.05 M CsPFf . in M iPF 5 /PC, to continue deposition for another 14 hours. Unlike the dendritic and mossy film deposNted in the control electrolyte, the micrograph in Figure 3B shows that a smooth lithiurn film was obtained after additional electrodeposition using embodiments of the 15 WO 2013/119322 PCT/US2012/070288 present invention. The roughness, pits, and valleys shown in Figure 3A have been filled by dense lithium deposits. The original needle-like dendritie whiskers have been convened to much smaller spherical particles which will also be buried if more lithium is deposited. 100421 Figure 4 includes S EM micrographs comparing the morphologies of the lithiun electrodes after repeated deposition/stripping cycles ( 2 nd 31 and 10t cycle) in cells using the control electrolyte (see Figures 4A. 4B, and 4C) and using electrolyte with a surface smoothing additive cormrising 0.05M Cs t (see Figures 41), 4E, and 4F). The large ithium dendrites and dark lithium particles are clearly observed on the lithium films deposited in the control electrolyte. in contrast, the morphologies of the lithium films deposited the Cs containing electrolyte still retain their dendrite free morphologies after repeated cycles, In all the films deposited with the additives, lithium films exhibit small spherical particles and smoother surfaces. This is in strong contrast with the needle-like dendrites grown in the control electrolyte. [0043] Electrolytes and methods described herein were also applied in rechargeable lithium metal batteries. Coin cells with LijILi4Ti 5 u()2 electrodes were assembled using the control electrolyte. Similar cells were also assembled with electrolytes containing a surface smoothing additive comprising 0.05 M Cs'. Figure 5 contains SEM nmierographs showing the morphologies of the lithium metal anodes after 100 charge/discharge cycles. Referring to Figure 5A, the lithium electrode in the cell with no additive exhibits clear surface roughness and formation of dendrites. However, as shown in Figure 5B, no dendritic lithium was observed on the lithium electrode in the cell with the surface-smoothing additive, even after 1 00 cycles, 16 WO 2013/119322 PCT/US2012/070288 [00441 Surface-snioothing additives comprising higher valence cautions can also be used. Examples include, but are not limited to, Sr" which have Et values of -2.958 V (assuming yl) versus a standard hydrogen potential. The lower activity of these nations can result in an effective E.RP lower than that of Li ions. The larger size and higher charge should be accounted for in the non-aqueous electrolyte. Lithium films were deposited using the control electrolyte along with electrolytes comprising 0.05 M Sr(F)2 Deposition from the electrolt conmrising 0.05 M Sr results in a lithium film that is smooth, free of dendrites. and void of Sr in/on the anode.. This again indicates that the activity coefficient for Sr" in these solutions is less than unity. {00451 Using this approach, C2 cations of the surface-smoothing additive are not reduced and deposited on the substrate. The (2 cations are not consumed because these nations exhibit an effective reduction potential lower than that of the reactant, In contrast., traditional electrodeposition can utilize additives having a reduction potential higher than that of the reactants: therefore, they will be reduced during the deposition process and "sacrificed or consumed," for example. as part of an SE1I filn or as an alloy to suppress dendrite growth. As a result, the additive concentration in the electrolyte will decrease with increasing charge/discharge cycles and the effect of the additives will quickly degrade. in contrast, the C2 cations described herein will forn a temporary electrostatic shield or "cloud" around the dendritic tips that retards further deposition of C1 in this region. This "cloud" will forn whenever a protrusion is initiated, but it will dissipate once applied voltage is removed or the protruson is eHininated. Accordingly, in some embodiments, the WO 2013/119322 PCT/US2012/070288 applied electrical potential is of a value that is less than, or equal to, the ERP of the reactants and greater than the effective ERP of the nations of (2. 100461 Lithium films having an SE1 layer on the surface and deposited using electrolytes comprising 0.05 M Cs', Rb' K', or S< additives were analyzed by x-ray photoelectron spectroscopy (XPS), Energy-dispersive X-ray spectroscopy (EDX) dot mapping, and Inductively coupled plasma atormie emission spectroscopy (ICP/AES) methods. XPS and D"X results did not show Cs, Rb, K. and Sr elements in the SE1 films within the detectable limits of the analysis instruments, In addition, ICP-AIES analysis did not identify (is, Rb, K, and Sr elements in the bulk of deposited lithium film (including the SEI layer on the surface) within detectable limits, 100471 Dendrite formation is not only a critical issue in rechargeable lithium metal batteries, but also an important issue in high power lithium ion batteries because lithium metal dendrites can grow at the anode surface when the lithium ions cannot move quickly enough to intercalate into the anode, which can ite or hard caon Ing rapid charging. In this case, the lithium dendrites can lead to short circuits and thermal runaway of the battery. Accordingly, a carbonaceous anode is described herein to demonstrate suppression of lithium dendrite growth in a lithium ion battery, Figure 6 compares tihe optical (6A and 61)) and SEM images (61. 6C, 6E, and 6F) of lithium particles formed on the hard carbon anode after it was charged to 300% of its theoretical capacity in a control electrolyte (without additives) and in an electrolyte having a surface smoothing additive comprising 0.05 M CsPlQAs ignificant amount of lithium metal was deposited on the surface of carbon electrode (see grey spots in Figure 6A) for the sample overcharged in the control electrolyte, Figures 613 and 6C show clear dendritic growth on the electrode 18 WO 2013/119322 PCT/US2012/070288 surface. hi contrast, no lithium metal deposition was observed on the surface of carbon electrode (see Figure 6D) for the sample overcharged in the electrolyte with 0.05M Cs* additive (the white line on the bottom of the carbon sample is due to an optical reflection. After renroving a small piece of carbon from the sample (see the circled area in Figure 6), it was foundd that excess lithium was preferentially grown on the bottom ox the carbon electrode as shown in Figures 6E and 6F. [00481 While a number of embodiments of tire present invention have been shown and described, it will be apparent to those skilled in the art that nrany changes and nodificlaions may be made without departing front the inventioi in its broader aspects. The appended clanrms, therefore, are intended to cover all such changes and modieations as 'hey fall lore., -. ,odnttications the yhfaal within the true spirit aind scope of the invention, 19
    权利要求:
    Claims (30)
    [1] 2. The electrolyte solution of Claim 1, wherein (:1 is a metallic material and the reactants comprise cations of C1.
    [2] 3. The electrolyte solution of Claim 2., wherein CI comprises a metal selected from the group consisting of Ui, -Na, Mg, Al, Sn, Ti. Fe, Ni, Cu., Zn. Ag, Pt, Au. and cominatns thereof
    [3] 4. The electrolyte solution of Claim 1, wherein CI comprises an electronic conductive polymer and tIhe reactants compri se monomers of the polyner.
    [4] 5. The electrolyte solution of Claim 1i, wherein the cations of C2 are metal cautions.
    [5] 6. The electrolyte solution of Claim 5, wherein the cations of C2 comprise a metal selected irom the group consisting of Cs. Rb. K, Ba, Sr, Ca, Li, and combinations thereof.
    [6] 7. The electrolyte solution of Claim 1, wherein the cations of C2 have an activity in solution such that the effective electrochemical reduction potential of nations of C2 is lower than that of the reactants. 20 WO 2013/119322 PCT/US2012/070288
    [7] 8. 'he electrolyte solution of Claim 1, wherein the cations of C2 have a concentration in solution such that the effective electrochemical reduction potential of nations of C2 is lower than that of the reactants.
    [8] 9. The electrolyte solution of Claim I, wherein the concentration of C2 cations is less than, or equal to, 30% of that of the reactants.
    [9] 10. The electrolyte solution of Claim I, wherein the concentration of £2 cations is less than, or equal to, 5% of that of the reactants. I. The e lectrolyte solution of Claim I, wherein the surface-smoothing additive comprises a anion selected from the group consisting of PF), AsF, B F1 N(SO2CF%)2 , N(SO2F)2 CF 3 SO 3 , C10 C~ Old. NO. SO and combiations thereof.
    [10] 12. The electrolyte solution of Claim 1, wherein the substrate is an electrode.
    [11] 13. The electrolyte solution of Claim 12, wherein the electrode conprises lithium.
    [12] 14. The electrolyte solution of Claim 2 wherein the electrode comprises carbon. 15 The electrolyte solution of Claim 12, wherein the electrode is an electrode in an energy storage device.
    [13] 16. The electrolyte solution of Claim 1, wherein the cations of C2 are not chemically or electrochemically reactive with respect to CI or the reactants.
    [14] 17. A method for improving surface smoothness during electrodeposition of a first conductive material (Cl) on a substrate surface, the method comprising: providing an electrolyte solution comprising reactants from which CI is synthesized and a soluble, surface-smoothing additive comprising cautions of a second conductive material (C2), wherein cations of C2 have an effective WO 2013/119322 PCT/US2012/070288 electrochemical reduction potential in the solution lower than that of the reactants; and applying an electrical potential thereby reducing the reactants and forming Ci on the substrate surface. 18 Ihe method of Claim 17, further comprising: accumulating cations of C2 at protrusions on the substrate surface. thereby forming an electrostatically shielded region near each protrusion; and temporarily repelling reactants from the electrostatically shielded regions.
    [15] 19. The method of Claim 17, wherein Cl is a metallic material and the reactants comprise nations of C 1.
    [16] 20. The method of Claim 19, wherein (1 is selected from the group consisting of Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, Ga, In, TI, Ge, Sn, Pb., As. Sb, Bi, Sc. Te, Bi. Po, Sc, Ti V, Cr, Mn. Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mco, Te. Ru, Rh, Pd, Ag, Cd, W, Pt, Au, 1-1g, and combinations thereof.
    [17] 21. The method of Claim 19, wherein C] cornpri ses Li,
    [18] 22. The method of Claim 17, wherein C1 comprises an electronic conductive polymer and the reactants comprise monomers of the polymer. 23 lhe method of claim 17, wherein the cations of (72 are metal cations. 24, The method of Claim 23, wherein the nations of C2 comprise a metal selected from the group consisting of Li, Cs, Rb, K, Ba, La, Sr. Ca, Ra, Zr, Te, B, Bi, Ta, la, Bu, S, Se, Nb, Na, Mg, Cu, Al, Fe, Zn, Ni, Ti, Sn, Sb, Mn, V, Ta, Cr, Au, Ge, Co, As, Ag, Mo. Si, W, Ru, I, Fe, Br, Re, Bi, Pt, Pd, and combinations thereof. 22 WO 2013/119322 PCT/US2012/070288
    [19] 25. The method of Claim 17, wherein the nations of C2 have an activity in solution such that the effective electrochemical reduction potential of the cations of C2 is lower than that of the reactants.
    [20] 26. The method of Claim 17. wherein the concentration of the cautions of C2 is less than, or equal to. 30% of that of the reactants.
    [21] 27. The method of Claim 17, wherein the concentration of the nations of C2 is less than, or equal to, 5% of that of the reactants.
    [22] 28. The method of Claim 17, wherein the surface-smoothing additive comprises an anion selected from the group consisting of PF6', AsF P, N(SO 2 C2), N(PSOAF), CFISOi, C104, U, CU, OH NO 3 , S and combinations thereof.
    [23] 29. The method of Claim 17, wherein the substrate is an electrode.
    [24] 30. The method of Claim 29, wherein the electrode comprises lithium.
    [25] 31. The method of Claim 29, wherein the electrode comprises carbon.
    [26] 32. The method of Claim 17, wherein the electrical potential applied is less than the electrochemical reduction potential of the reactant and greater than the effective electrochemical reduction potential of the cations of C2.
    [27] 33. A method for improving surface snootiness during electrodepositiorn of lithium on a substrate surface, the method comprising: providing an electrolyte solution comprising lithium nations and a soluble, surface-smoothing additive comprising cations of a second conductive material (C2) selected from the group consisting of cesium, rubidium, potassim, strontium, barium, calcium, and combinations thereof, wherein cations of (22 have an activity in solution such that the effective 23 WO 2013/119322 PCT/US2012/070288 electrochemical reduction potential of the nations oftC2 is lower than that of the lithium cations; applying an electrical potential thereby reducing the lithium catons and forming lithium on the substrate surface; accunulating nations of C2 at protrusions on the substrate surface, thereby forming an electrostatically shielded region near each protrusion; and temporarily repelling the lithium cations from the electrostatically shielded regions.
    [28] 34. The method of Claim 33, wherein the cations of C2 have a concentration in the electrolyte that is less than, or equal to, 30% of that of the lithium nations.
    [29] 35. The method of Claim 33, wherein the cations of C2 have a concentraton in the electrolyte that is less than, or equal to, 5% of that of the lithium cations, 36 The method of Claim 33,. wherein the surface-srnoothing additive comprises an anion comprising Pi anion. 37 The method of Claim 33, wherein the substrate is a battery anode comprising lithium or a battery anode comprising carbon.
    [30] 38.l'he method of Claim 33, wherein the electrical potential applied is less than the electrochemical reduction potential of the lithium cations and greater than the effective electrochemical reduction potential of the cations of C2
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    同族专利:
    公开号 | 公开日
    EP2812466A4|2015-09-16|
    US20150152566A1|2015-06-04|
    US20130199936A1|2013-08-08|
    BR112014016918A8|2017-07-04|
    BR112014016918A2|2017-06-13|
    KR20140120882A|2014-10-14|
    CN104040034B|2017-08-25|
    WO2013119322A1|2013-08-15|
    CN104040034A|2014-09-10|
    EP2812466A1|2014-12-17|
    AU2012369141B2|2016-11-10|
    CA2856741A1|2013-08-15|
    US8980460B2|2015-03-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2907656A|1953-11-12|1959-10-06|Chrome Steel Plate Corp|Lithographic plates|
    US3677913A|1971-04-01|1972-07-18|M & T Chemicals Inc|Nickel plating|
    US4225407A|1979-04-04|1980-09-30|The Dow Chemical Company|Cathodic electrodeposition of polymers onto a conductive surface|
    US4331517A|1981-04-02|1982-05-25|Ppg Industries, Inc.|Method of preparing a cathode by high and low temperature electroplating of catalytic and sacrificial metals, and electrode prepared thereby|
    US4615773A|1984-05-07|1986-10-07|State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Portland State University|Chromium-iron alloy plating from a solution containing both hexavalent and trivalent chromium|
    US4695521A|1985-06-27|1987-09-22|Allied Corporation|Conjugated polymer as substrate for the plating of alkali metal in a nonaqueous secondary battery|
    US5085955A|1990-11-21|1992-02-04|The Dow Chemical Company|Non-aqueous electrochemical cell|
    US5385661A|1993-09-17|1995-01-31|International Business Machines Corporation|Acid electrolyte solution and process for the electrodeposition of copper-rich alloys exploiting the phenomenon of underpotential deposition|
    JP3309719B2|1996-07-10|2002-07-29|松下電器産業株式会社|Non-aqueous electrolyte secondary battery|
    KR100390890B1|1998-11-14|2003-10-08|주식회사 하이닉스반도체|A method for forming a conductive layer and an apparatus thereof|
    US20020192546A1|2001-06-07|2002-12-19|Zhenhua Mao|Multi-salt electrolyte for electrochemical applications|
    CN100412236C|2002-03-13|2008-08-20|三菱化学株式会社|Gold plating solution and gold plating method|
    JP2003272703A|2002-03-20|2003-09-26|Fuji Photo Film Co Ltd|Electrolyte and nonaqueous electrolyte secondary battery|
    US20090197168A1|2005-11-04|2009-08-06|Tetsuo Nishida|Storage element|
    JP2009054354A|2007-08-24|2009-03-12|Sony Corp|Nonaqueous electrolytic solution composition, and nonaqueous electrolytic solution secondary battery|
    US9184436B2|2012-02-07|2015-11-10|Battelle Memorial Institute|Methods and energy storage devices utilizing electrolytes having surface-smoothing additives|
    US20130202920A1|2012-02-07|2013-08-08|Battelle Memorial Institute|Dendrite-Inhibiting Salts in Electrolytes of Energy Storage Devices|US9184436B2|2012-02-07|2015-11-10|Battelle Memorial Institute|Methods and energy storage devices utilizing electrolytes having surface-smoothing additives|
    US9865900B2|2012-02-07|2018-01-09|Battelle Memorial Institute|Solid electrolyte interphase film-suppression additives|
    US20150233011A1|2014-02-19|2015-08-20|Macdermid Acumen, Inc.|Treatment for Electroplating Racks to Avoid Rack Metallization|
    EP3353844A4|2015-03-27|2020-01-08|Mason K. Harrup|All-inorganic solvents for electrolytes|
    US10707531B1|2016-09-27|2020-07-07|New Dominion Enterprises Inc.|All-inorganic solvents for electrolytes|
    KR101990618B1|2017-04-14|2019-06-18|주식회사 엘지화학|Electrolyte Plating Solution for Lithium Metal and Method for Preparing Lithium Metal Electrode|
    US20210050601A1|2017-05-16|2021-02-18|Arizona Board Of Regents On Behalf Of Arizona State University|Three-dimensional soft electrode for lithium metal batteries|
    CN109180181B|2018-09-28|2020-10-27|西安交通大学|Lead-free relaxation antiferroelectric ceramic energy storage material and preparation method thereof|
    CN111893526A|2020-08-06|2020-11-06|中国科学技术大学|Nano-silver alloy modified substrate and preparation method and application thereof|
    法律状态:
    2017-03-09| FGA| Letters patent sealed or granted (standard patent)|
    2018-07-12| MK14| Patent ceased section 143(a) (annual fees not paid) or expired|
    优先权:
    申请号 | 申请日 | 专利标题
    US13/367,508|US20130202920A1|2012-02-07|2012-02-07|Dendrite-Inhibiting Salts in Electrolytes of Energy Storage Devices|
    US13/367,508||2012-02-07||
    US13/495,727||2012-06-13||
    US13/495,727|US8980460B2|2012-02-07|2012-06-13|Methods and electrolytes for electrodeposition of smooth films|
    PCT/US2012/070288|WO2013119322A1|2012-02-07|2012-12-18|Methods and electrolytes for electrodeposition of smooth films|
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