WO2021159209A1 - Électrodes à surface modifiée, procédés de préparation, et utilisations dans des cellules électrochimiques - Google Patents
Électrodes à surface modifiée, procédés de préparation, et utilisations dans des cellules électrochimiques Download PDFInfo
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Definitions
- the present application relates to lithium electrodes having at least one modified surface, to their manufacturing processes and to electrochemical cells comprising them.
- the liquid electrolytes used in lithium-ion batteries are flammable and slowly degrade to form a passivation layer on the surface of the lithium film or solid electrolyte interface (SEI for “solid electrolyte interface” or “solid electrolyte interphase” in English) irreversibly consuming lithium, which decreases the coulombic efficiency of the battery.
- SEI solid electrolyte interface
- solid electrolyte interphase solid electrolyte interphase
- a simple and more industrially transposable method for protecting the lithium surface is to cover its surface with a polymer or a polymer / lithium salt mixture by coating by spraying, by immersion, using a centrifuge or again using the so-called doctor blade method (N. Delaporte, et al., Front. Mater., 2019, 6, 267).
- the polymer chosen must then be stable against lithium and an ionic conductor at low temperature.
- the polymer layer deposited on the surface of lithium should be comparable to the solid polymer electrolytes (SPE) generally reported in the literature, which have a low glass transition (TV) in order to to remain rubbery at room temperature and to maintain a conductivity of lithium similar to that of a liquid electrolyte.
- SPE solid polymer electrolytes
- the polymer In order to adapt to the deformation of lithium during cycling and above all to avoid the formation of lithium dendrites, the polymer must have good flexibility and must be characterized by a high Young's modulus.
- polymers used in this type of protective layer include polyacrylic acid (PAA) (N.-W. Li, et al., Angew. Chem. Int. Ed., 2018, 57, 1505-1509), poly (vinylidene-co-acrylonitrile carbonate) (SM Choi et al., J. Power Sources, 2013, 244, 363-368), poly (ethylene glycol) dimethacrylate (YM Lee, et al., J. Power Sources, 2003, 119-121, 964-972), the PEDOT-co-PEG copolymer (G. Ma, et al., J. Mater. Chem. A, 2014, 2, 19355-19359 and IS Kang, et al.
- PAA polyacrylic acid
- SCA polymer
- SM Choi et al. J. Power Sources, 2013, 244, 363-368
- poly (ethylene glycol) dimethacrylate YM Lee, et al., J. Power Sources,
- a 20 ⁇ m protective layer composed of particles of ALCte (1.7 ⁇ m in average diameter) and polyvinylidene-hexafluoropropylene fluoride (PVDF-HFP) deposited on the surface of lithium has been proposed to improve the service life of the lithium.
- lithium-oxygen batteries DJ Lee, et al., Electrochem. Commun., 2014, 40, 45-48.
- the effect of a similarly modified lithium has also been studied by Gao and colleagues (HK Jing et al., J. Mater. Chem. A, 2015, 3, 12213-12219), although the emphasis is been focused on improving lithium-sulfur batteries.
- 100nm ALCte spheres were used with PVDF as a binder and the mixture prepared in DMF solvent was spread by centrifugation on a lithium foil. The batteries were then fitted with a liquid electrolyte.
- a 25 ⁇ m porous layer of polyimide with GAI2O3 as filler (particle size about 10 nm) in order to limit lithium growth has also been proposed (see Z. Peng et al., J. Mater. Chem. A, 2016, 4, 2427-2432).
- This method includes the formation of a film called "skin layer” by bringing lithium into contact with an additive present in the liquid electrolyte (such as carbonate. fluoroethylene (FEC), vinylene carbonate (VC) or hexamethylene diisocyanate (HDI)).
- FEC fluoroethylene
- VC vinylene carbonate
- HDI hexamethylene diisocyanate
- Cu / LiFePO4 electrochemical cells comprising this liquid electrolyte were tested to demonstrate the utility of the polyimide / Al2O3 layer in inhibiting dendrite formation and electrolyte degradation.
- the protective layers described in the previous three paragraphs are porous and suitable for use with a liquid electrolyte, which can penetrate them. This type of layer is therefore not suitable for use with a solid electrolyte which must be able to be in intimate contact with the surface of the electrode (or of its protective layer) and allow the conduction of the electrolyte ions. towards the active electrode material.
- the present technology relates to an electrode comprising a metallic film modified by a thin layer, in which:
- the metallic film comprises lithium or an alloy comprising lithium, the metallic film comprising a first and a second surface;
- the thin layer comprises an inorganic compound in a solvating polymer (for example, a solid polymer and / or a crosslinked polymer), the thin layer being disposed on the first surface of the metal film and having an average thickness of about 10 ⁇ m or less (or between about 0.5 pm and about 10pm, or between about 1 pm and about 10pm, or between about 2pm and about 8pm, or between about 2pm and about 7pm, or between 2pm and about 5pm), the inorganic compound being present in the thin film at a concentration between about 40% and about 90% by mass.
- a solvating polymer for example, a solid polymer and / or a crosslinked polymer
- the metallic film comprises lithium comprising less than 1000 ppm (or less than 0.1% by weight) of impurities.
- the metallic film comprises an alloy of lithium and an element selected from alkali metals other than lithium (such as Na, K, Rb, and Cs), alkaline earth metals (such as Mg, Ca, Sr, and Ba), rare earth metals (such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium, nickel and germanium (eg, Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, In, Tl, Ni, or Ge
- the metal film further comprises a passivation layer on the first surface, the latter being in contact with the thin layer, for example, the passivation layer comprising a compound chosen from a silane, a phosphonate , a borate or an inorganic compound (such as LiF, LbN, LbP, LiNC, LbPC).
- a passivation layer comprising a compound chosen from a silane, a phosphonate , a borate or an inorganic compound (such as LiF, LbN, LbP, LiNC, LbPC).
- the first surface of the metal film is modified by pre-stamping.
- the inorganic compound is in the form of particles (eg, spherical, rod-shaped, needle-like, etc.).
- the average particle size is less than 1 ⁇ m, less than 500nm, or less than 300nm, or less than 200nm, or between 1nm and 500nm, or between 10nm and 500nm, or between 50nm and 500nm, or between 100nm and 500nm, or between 1 nm and 300nm, or between 10nm and 300nm, or between 50nm and 300nm, or between 100nm and 300nm, or between 1 nm and 200nm, or between 10nm and 200nm, or also between 50nm and 200nm, or between 100nm and 200nm, or between 1 nm and 100nm, or between 10nm and 100nm, or alternatively between 25nm and 100nm, or between 50nm and 100nm.
- the inorganic compound comprises a ceramic.
- the inorganic compound is chosen from Al2O3, Mg2B205, Na20-2B203, xMg0 yB203-zH20, T1O2, ZrO2, ZnO, T12O3, S1O2, Cr 2 0 3 , Ce0 2 , B2O3, B2O, SrBUTUOis, LLTO, LLZO, LAGP, LATP, Fe 2 0 3 , BaTiOs, Y-L1AIO2, molecular sieves and zeolites (eg, aluminosilicate, silica mesoporous), sulfide ceramics (such as U7P3S11), glass-ceramics (such as LIPON, etc.), and other ceramics, as well as their combinations.
- zeolites eg, aluminosilicate, silica mesoporous
- sulfide ceramics such as U7P3S11
- the particles of the inorganic compound further comprise organic groups grafted to their surface covalently, for example, said groups being chosen from crosslinkable groups (such as organic groups comprising acrylate, methacrylate, etc. vinyl, glycidyl, mercapto, etc.), aryl groups, alkylene oxide or poly (alkylene oxide) groups, and other organic groups.
- crosslinkable groups such as organic groups comprising acrylate, methacrylate, etc. vinyl, glycidyl, mercapto, etc.
- aryl groups alkylene oxide or poly (alkylene oxide) groups, and other organic groups.
- the particles of the inorganic compound have a small specific surface area (eg, less than 80 m 2 / g, or less than 40 m 2 / g) and, preferably, the inorganic compound is present in the layer. thin at a concentration of between about 65% and about 90% by weight, or between about 70% and about 85% by weight.
- the particles of the inorganic compound have a large specific surface area (for example, of 80 m 2 / g and more, or of 120 m 2 / g and more) and, preferably, the inorganic compound is present in the thin layer at a concentration of between about 40% and about 65% by weight, or between about 45% and about 55% by weight.
- the solvating polymer is chosen from linear or branched polyether polymers (for example, PEO, PPO, or EO / PO copolymer), poly (dimethylsiloxanes), poly (alkylene carbonates), poly (alkylene sulfones), poly (alkylene sulfonamides), polyurethanes, poly (vinyl alcohol), polyacrylonitriles, polymethyl methacrylates, and their copolymers, optionally comprising crosslinked units originating from crosslinkable functions (such as acrylate and methacrylate functions , vinyls, glycidyls, mercapto, etc.).
- linear or branched polyether polymers for example, PEO, PPO, or EO / PO copolymer
- poly (alkylene carbonates) poly (alkylene sulfones), poly (alkylene sulfonamides)
- polyurethanes poly (vinyl alcohol
- the thin film further comprises a lithium salt, for example chosen from lithium hexafluorophosphate (LiPFe), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), bis (fluorosulfonyl) imide lithium (LiFSI), 2- lithium trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1, 2,3-triazolate (LiDCTA), lithium bis (pentafluoroethylsulfonyl) imide (LiBETI), tetrafluoroborate lithium (L1BF4), lithium bis (oxalato) borate (LiBOB), lithium nitrate (UNO3), lithium chloride (LiCI), lithium bromide (LiBr), lithium fluoride (LiF), lithium lithium perchlorate (UCIO4), lithium hexafluoroarsenate (LiAsFe), lithium trifluo
- the electrode further comprises a current collector in contact with the second surface of the metal film.
- Another aspect relates to an electrode comprising a film of electrode material modified by a thin film, wherein:
- the film of electrode material comprises an electrochemically active material, optionally a binder, and optionally an electronically conductive material, the film of electrode material comprising a first and a second surface;
- the thin layer comprises an inorganic compound in a solvating polymer (for example, a solid polymer and / or a crosslinked polymer), the thin layer being arranged on the first surface of the metal film and having an average thickness of about 10 ⁇ m (or between about 0.5 pm and about 10pm, or between about 1pm and about 10pm, or between about 2pm and about 8pm, or between about 2pm and about 7pm, or between 2pm and about 5pm) or less, the inorganic compound being present in the thin film at a concentration of between about 40% and about 90% by weight.
- the elements (inorganic compound, polymer, and optionally a salt) of the thin layer defined in the embodiments of the preceding aspect are also envisaged.
- the electrode further includes a current collector in contact with the second surface of the film of electrode material.
- the electrochemically active material is chosen from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides.
- the electrochemically active material is in the form of possibly coated particles (eg, polymer, ceramic, carbon, or a combination of two or more thereof).
- the present document describes an electrode-electrolyte component comprising an electrode as defined here and a solid electrolyte.
- the solid electrolyte comprises at least one solvating polymer and a lithium salt.
- the electrolyte solvating polymer is chosen from linear or branched polyether polymers (for example, PEO, PPO, or EO / PO copolymer), and optionally comprising crosslinkable units), poly (dimethylsiloxanes) , poly (alkylene carbonates), poly (alkylene sulfones), poly (alkylene sulfonamides), polyurethanes, poly (vinyl alcohol), polyacrylonitriles, polymethyl methacrylates, and their copolymers, the solvating polymer optionally being crosslinked .
- the lithium salt of the electrolyte is chosen from lithium hexafluorophosphate (LiPFe), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI) , lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1, 2,3-triazolate (LiDCTA), lithium bis (pentafluoroethylsulfonyl) imide (LiBETI) , lithium tetrafluoroborate (L1BF4), lithium bis (oxalato) borate (LiBOB), lithium nitrate (UNO3), lithium chloride (LiCI), lithium bromide (LiBr), lithium fluoride ( LiF), lithium perchlorate (UCIO4), lithium hexafluoroarsenate (LiAsFe), lithium trifluo
- an additional aspect of this document relates to an electrochemical cell comprising a negative electrode, a positive electrode, and a solid electrolyte, wherein at least one of the negative electrode and the positive electrode is as described herein.
- the negative electrode is as described herein.
- the positive electrode is as described herein.
- the negative electrode and the positive electrode are as described herein.
- the electrolyte is as defined above.
- the present technology also comprises an electrochemical accumulator (for example, a lithium battery or a lithium-ion battery) comprising at least one electrochemical cell as described here, as well as their use in nomadic devices (such as mobile telephones, cameras, tablets or laptops), in electric or hybrid vehicles, or in renewable energy storage.
- Figure 1 shows a photograph of a section of a piece of lithium having a thin ceramic layer (85% AI2O3 spherical).
- Figure 2 shows the scanning electron microscopy (SEM) images of a thin film comprising 50% Mg2B20s on a LiAI alloy (a) and its corresponding chemical map: (b) magnesium, (c) boron, (d) oxygen, (e) sulfur, (f) fluorine, and (g) carbon.
- SEM scanning electron microscopy
- Figure 3 shows the SEM images of a thin layer comprising a ceramic (85% AI2O3 spherical) on a LiMg alloy and showing one layer rich in ceramic, the other rich in polymer and ceramic.
- Figure 4 shows the SEM images of a thin film comprising 50% AI2O3 in the form of needles (a) on a LiAI alloy and its corresponding chemical mapping: (b) C, Al, O, S and electron distribution, (c) aluminum, (d) oxygen, and (e) carbon.
- Figure 5 shows the SEM images of an SPE (ca.15-20 ⁇ m) comprising an AI2O3 spherical ceramic (70% by mass) on a LiAI alloy (top image) and the distribution of S, C, Al, O and electrons (bottom image).
- Figure 6 shows the SEM images of an SPE (approximately 10-15 ⁇ m) comprising an AI2O3 spherical ceramic (85% by mass) on a LiAI alloy (top image) and the distribution of S, C, Al, O and electrons (bottom image).
- Figure 7 shows the SEM images of a Li / SPE / Li symmetrical cell made with standard unmodified Li ((a) and (b)) and its chemical mapping: (c) carbon, (d) oxygen, ( e) fluorine, (f) lithium, (g) sulfur, and (h) aluminum (Al from the support behind the sample).
- Figure 8 shows (a) the spectroscopic impedance measurements for 4 cells; (b) cycling stability results at a rate of C / 4 (charge and discharge) for two cells (including two cycles of C / 24 training); and (c) resistance results at different imposed currents (C / 24 to 1 C) for two independent cells, all cells being symmetrical and assembled with standard pure lithium.
- Figure 9 shows (a) the spectroscopic impedance measurements for 4 cells; (b) cycling stability results at a rate of C / 4 (charge and discharge) for two cells (including two cycles of C / 24 training); and (c) resistance results at different imposed currents (C / 24 to 1 C) for two independent cells, all the cells being symmetrical and assembled with a LiAI lithium alloy.
- Figure 10 shows (a) the spectroscopic impedance measurements for 4 cells; (b) cycling stability results at a rate of C / 4 (charge and discharge) for two cells (including two cycles of C / 24 training); and (c) resistance results at different imposed currents (C / 24 to 1 C) for two independent cells, all the cells being symmetrical and assembled with a LiMg lithium alloy.
- Figure 11 shows the SEM images of a LiAI / SPE / LiAI symmetrical battery made with standard Li modified with spherical AI2O3 (85% by mass) at different magnifications.
- Figure 12 shows SEM images of a LiAI / SPE / LiAI symmetrical battery made with standard Li modified with spherical AI2O3 (85% by mass) (in (a)) and its chemical mapping: (b) oxygen, (c) aluminum, (d) carbon, (e) fluorine, (f) sulfur, and (g) lithium.
- Figure 13 presents the results (a) of resistance to different imposed currents (C / 24 at 1 C) for a cell assembled with two LiAI; (b) and (c) spectroscopic impedance measurements carried out at 50 ° C for 2 cells after assembly and after each cycling speed, all the cells being symmetrical with LiAI modified with spherical AI2O3 (85% by mass).
- Figure 14 shows the results (a) and (b) of a cycling stability study at a rate of 1 C (charge and discharge) with a return to a rate of C / 4 for 3 cycles for two independent cells; (c) and (d) spectroscopic impedance measurements taken every three cycles at 50 ° C for the same cells, all cells being symmetrical with LiAI modified with spherical AI2O3 (85% by mass).
- Figure 15 shows the SEM images of a LiAI / SPE / LiAI symmetrical cell manufactured with standard Li modified with spherical AI2O3 (85% by mass) (in (a)) and its chemical mapping: (b) oxygen, ( c) carbon, (d) aluminum, (e) fluorine, (f) sulfur, and (g) lithium (short-circuited symmetrical cell).
- Figure 16 shows (a) the spectroscopic impedance measurements for 4 cells; (b) cycling stability results at a rate of C / 4 (charge and discharge) for two cells (including two cycles of C / 24 training); and (c) resistance results at different imposed currents (C / 24 to 1 C) for two independent cells, all cells being symmetrical and assembled with lithium modified with spherical AI2O3 (85% by mass).
- Figure 17 shows (a) the spectroscopic impedance measurements for 3 cells; (b) cycling stability results at a rate of C / 4 (charge and discharge) for a cell (including two cycles of C / 24 training); and (c) resistance results at different imposed currents (C / 24 to 1 C) for two cells independent, all the cells being symmetrical and assembled with lithium modified with AI2O3 in needles (50% by mass).
- Figure 18 shows in (a) a diagram illustrating the configuration of cells assembled with LiAI modified with needle AI2O3 (50% by mass) on one side and unmodified LiAI on the other, and the results obtained with these cells including (b) spectroscopic impedance measurements for 4 cells; (c) cycling stability results at a rate of C / 4 (charge and discharge) for two cells (including two cycles of C / 24 training); and (d) resistance results at different imposed currents (C / 24 to 1C) for two independent cells ,.
- Figure 19 shows SEM images of a battery (not shorted) assembled with LiAI modified with needle AI2O3 (50% by mass) on one side and unmodified LiAI on the other (in (a) and (b)) and its chemical mapping: (c) carbon, (d) oxygen, (e) aluminum, (f) fluorine, (g) sulfur, and (h) lithium.
- Figure 20 shows SEM images of a (shorted) battery assembled with LiAI modified with needle AI2O3 (50% by mass) on one side and unmodified LiAI on the other (in (a), (b) and (c)) and its chemical mapping: (d) carbon, (e) oxygen, (f) fluorine, (g) aluminum, (h) sulfur, and (i) lithium.
- Figure 21 shows (a) a schematic illustration of the assembly of a cell where a LiAI film has a layer approximately 25 ⁇ m thick directly deposited on its surface and containing 85% spherical ALCte; (b) spectroscopic impedance measurements taken at 50 ° C for 2 independent cells; and (c) the first two C / 24 training cycles for two stacks assembled according to the schematic representation in (a).
- Figure 22 shows the first two charge / discharge curves obtained at 80 ° C and C / 24 for LFP / SPE / LiAI batteries assembled with (a) a LiAI anode without modification; (b) a LiAI anode with a layer comprising 50% needle-shaped ALCte; and (c) a LiAI anode with a layer comprising 85% spherical A Cte.
- Figure 23 shows the results of galvanostatic cycling obtained at 50 ° C and in C / 6 (2 cycles in C / 12 every 20 cycles in C / 6) for LFP / SPE / LiAI batteries assembled with (a) an anode of LiAI without modification; (b) a needle-shaped LiAI with 50% ALCte anode; and (c) a LiAI anode with a layer comprising 85% spherical ALCte.
- Figure 24 shows the results of galvanostatic cycling obtained at 50 ° C and in C / 6 (2 cycles in C / 12 every 20 cycles in C / 6) for LFP / SPE / LiMg batteries assembled with (a) an anode of LiMg without modification; and (b) a LiMg anode with a layer comprising 85% spherical ALCte.
- Figure 25 shows the results of galvanostatic cycling obtained at 50 ° C and in C / 6 (2 cycles in C / 12 every 20 cycles in C / 6) for LFP / SPE / Li batteries assembled with (a) an anode of Li without modification; and (b) a Li anode with a layer containing 85% spherical ALCte.
- Figure 26 shows SEM images of a thin layer of a polymer and a salt (without ceramic) on a composite material comprising LiFePC (x500 on the left and x5000 on the right).
- Figure 27 shows the SEM images of a thin layer of a polymer and a salt (without ceramic) on a composite material comprising LiFePC (in (a)) and its corresponding chemical map: (b) iron, (c) phosphorus, (d) oxygen, (e) carbon, and (f) sulfur.
- Figure 28 shows a SEM image of the wafer of the LFP cathode with a thin layer of polymer + salt (20: 1 O: Li) containing 50 wt% spherical ALCte.
- Figure 29 shows SEM images of the slice of the LFP cathode with a thin layer of polymer + salt (20: 1 O: Li) containing 50% by mass of ALCte spherical (in (a)) and its corresponding chemical mapping: (b) phosphorus, (c) iron, (d) oxygen, (e) carbon and (f) aluminum.
- Figure 30 shows the results of (a) long cycling (charge: C / 6, discharge: C / 3) and (b) cycling at different speeds C at 80 ° C, for LFP / SPE / Li batteries assembled with a Standard LiAI (unmodified), a standard SPE (polymer + LiTFSI with O: Li ratio of 30: 1, 20 ⁇ m thick) and a cathode of LFP with (LFP overcoated) and without (LFP_REF) ceramic thin film ( 50% AI2O3).
- alkyl refers to saturated hydrocarbon groups having 1 to 20 carbon atoms, including linear or branched alkyl groups.
- alkyls can include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, isobutyl and the like.
- an “alkylene” group denotes an alkyl group located between two other groups. Examples of alkylene groups include methylene, ethylene, propylene, etc.
- C1-C n alkyl and C1-Cnalkylene refer to an alkyl or alkylene group having from 1 to the number "n" of carbon atoms.
- this document therefore presents a process for modifying the surface of an electrode film.
- this electrode film consists of a metal film, for example comprising lithium or an alloy predominantly comprising lithium.
- the electrode film comprises an electrochemically active material, optionally a binder, and optionally an electronically conductive material.
- modification of the surface is meant the application of a thin ion conductive layer and serving as a barrier to the formation of dendrites without, however, reacting substantially with the surface of the electrode film, the elements of the thin film being mostly non-reactive.
- the surface of the electrode film is modified by applying to one of its surfaces a thin layer comprising an inorganic compound in a solvating polymer, preferably an optionally crosslinked solid polymer.
- the thin layer is provided on the first surface of the metal film and has an average thickness of about 10 ⁇ m or less.
- the inorganic compound is present in the thin film at a concentration ranging from about 40% to about 90% by weight.
- the inorganic compound is preferably in the form of particles (eg, spherical, rods, needles, etc.).
- the average particle size is preferably nanometric, for example, less than 1 ⁇ m, less than 500nm, or less than 300nm, or less than 200nm, or between 1 nm and 500nm, or between 10nm and 500nm, or alternatively between 50nm and 500nm, or between 100nm and 500nm, or between 1 nm and 300nm, or between 10nm and 300nm, or between 50nm and 300nm, or between 100nm and 300nm, or between 1 nm and 200nm, or between 10nm and 200nm, or also between 50nm and 200nm, or between 10Onm and 200nm, or between 1 nm and 10Onm, or between 10nm and 100nm, or alternatively between 25nm and 100nm, or between 50nm and 100nm.
- Non-limiting examples of inorganic compounds include compounds or ceramics such as AI2O3, Mg2B20s, Na20-2B203, xMgO yB203 zhteO, Ti02, ZrO2, ZnO, T12O3, S1O2, Cr203, Ce02, B2O3, B2O, SrBUTUOis, LLTO, LLTO, LLTO, LLTO, LLTO , LAGP, LATP, Fe 2 0 3 , BaTiOs, Y-L1AIO2, molecular sieves and zeolites (eg, aluminosilicate, mesoporous silica, etc.), sulfide ceramics (such as L17P3S11), glass-ceramics (such as LIPON, etc.), and other ceramics, as well as their combinations.
- the surface of the particles of the inorganic compound can also be modified by organic groups grafted onto their surface covalently.
- the groups can be chosen from crosslinkable groups, aryl groups, alkylene oxide or poly (alkylene oxide) groups, and other organic groups, these being grafted directly onto the surface or via a group. link.
- crosslinkable groups can comprise glycidyl, mercapto, vinyl, acrylate or methacrylate functions.
- Scheme 1 shows an example of a method of grafting silanes comprising propyl methacrylate groups.
- the particles of the inorganic compound have a small specific surface area (eg, less than 80 m 2 / g, or less than 40 m 2 / g).
- the concentration of inorganic compound in the thin film can then be relatively high, for example, between about 65% and about 90% by weight, or between about 70% and about 85% by weight.
- the particles of the inorganic compound have a large specific surface area (for example, 80 m 2 / g and more, or 120 m 2 / g and more).
- the greater porosity of the inorganic compound may then require a greater amount of polymer and the concentration of the inorganic compound in the thin layer will then be in the range of 40% to about 65% by mass, or between about 45% and about 55% by mass.
- the average thickness of the thin film is such that it is considered a modification of the electrode surface rather than an electrolyte layer.
- the average thin film thickness is less than 10pm. For example, this is between around 0.5 pm and around 10pm, or between around 1 pm and around 10pm, or between around 2pm and around 8pm, or between around 2pm and around 7pm, or between 2pm and around 5pm .
- the polymer present in the layer is a crosslinked polymer comprising ion solvating units, in particular lithium ions.
- polymers solvators include linear or branched polyether polymers (eg, PEO, PPO, or EO / PO copolymer), poly (dimethylsiloxanes), poly (alkylene carbonates), poly (alkylene sulfones), poly (alkylene sulfonamides), polyurethanes, poly (vinyl alcohol), polyacrylonitriles, polymethyl methacrylates, and their copolymers, and optionally comprising crosslinked units originating from crosslinkable functions (such as acrylates, methacrylates, vinyls, glycidyls, mercapto, etc.) .
- crosslinkable functions such as acrylates, methacrylates, vinyls, glycidyls, mercapto, etc.
- the thin layer further comprises a lithium salt.
- lithium salts include lithium hexafluorophosphate (LiPFe), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), 2-trifluoromethyl-4,5 lithium-dicyano-imidazolate (LiTDI), lithium 4,5-dicyano-1, 2,3-triazolate (LiDCTA), lithium bis (pentafluoroethylsulfonyl) imide (LiBETI), lithium tetrafluoroborate (L1BF4), lithium bis (oxalato) borate (LiBOB), lithium nitrate (UNO3), lithium chloride (LiCI), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (UCIO4 ), lithium hexafluoroarsenate (L
- LiPFe lithium hex
- the electrode can comprise a metallic film of lithium or an alloy comprising lithium, optionally on a current collector.
- the metallic film is a lithium film
- the latter consists of lithium comprising less than 1000 ppm (or less than 0.1% by mass) of impurities.
- a lithium alloy can comprise at least 75% by weight of lithium, or between 85% and 99.9% by weight of lithium.
- the alloy can then comprise an element chosen from alkali metals other than lithium (such as Na, K, Rb, and Cs), alkaline earth metals (such as Mg, Ca, Sr, and Ba), rare earth metals (such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium, nickel and germanium (by example, Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, In, Tl, Ni, or Ge).
- alkali metals other than lithium such as Na, K, Rb, and Cs
- alkaline earth metals such as Mg, Ca,
- the metallic film can also include a passivation layer on the first surface, the latter being in contact with the thin layer.
- the passivation layer comprises a compound selected from a silane, a phosphonate, a borate or an inorganic compound (such as LiF, LbN, LbP, LiNC, LbPC).
- the passivation layer is formed on the metal film before adding the thin layer.
- the surface of the metal film can also be treated before the application of the thin layer, for example by stamping.
- the electrode when the electrode is not a metallic film, the latter comprises an electrochemically active material (for example, a positive electrode), optionally a binder, and optionally an electronically conductive material, optionally on a current collector.
- the electrochemically active material can be chosen from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides, but also other materials such as sulfur, selenium or Elemental iodine, iron (III) fluoride, copper (II) fluoride, lithium iodide, and carbon-based active materials such as graphite.
- Examples of electronically conductive materials that can be included in the electrode material include carbon black (such as Ketjen TM carbon, acetylene black, etc.) graphite, graphene, carbon nanotubes, fibers carbon (including carbon nanofibers, carbon fibers formed in the gas phase (VGCF), etc.), non-powdery carbon obtained by carbonization of an organic precursor (for example, as a coating on particles) , or a combination of at least two of these.
- carbon black such as Ketjen TM carbon, acetylene black, etc.
- graphite graphene
- carbon nanotubes fibers carbon (including carbon nanofibers, carbon fibers formed in the gas phase (VGCF), etc.
- non-powdery carbon obtained by carbonization of an organic precursor (for example, as a coating on particles) , or a combination of at least two of these.
- Non-limiting examples of electrode material binders include the polymer binders described above in connection with the thin film or below for the electrolyte, but also rubber-type binders such as SBR (styrene-butadiene rubber ), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CH R (epichlorohydrin rubber), and ACM (acrylate rubber), or fluoropolymer type binders such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof. Certain binders, such as those of the rubber type, can also include an additive such as CMC (carboxymethylcellulose).
- CMC carboxymethylcellulose
- the electrode material may also be present in the electrode material, such as lithium salts or inorganic particles of ceramic or glass type, or other compatible active materials (for example, sulfur).
- the metallic film or electrode material can be applied to a current collector (eg, aluminum, copper).
- the current collector is made of aluminum covered with carbon.
- the electrode can be self-supporting.
- This document also relates to a process for the preparation of a surface modified electrode as described here.
- This process comprises (i) mixing an inorganic compound and a solvating polymer optionally crosslinkable in a solvent, optionally comprising a salt and / or optionally a crosslinking agent; (ii) spreading the mixture obtained in (i) on the surface of the electrode; (iii) removal of the solvent; and optionally (iv) crosslinking of the polymer (for example ionically, thermally or by irradiation). Steps (iii) and (iv) can also be reversed in certain cases.
- steps (ii), (iii) and / or (iv) are preferably carried out under vacuum or in an anhydrous chamber filled with an inert gas such as argon.
- the process can exclude the presence of solvent and step (iii) can be avoided.
- Spreading can be carried out by conventional methods, for example, using a roller, such as a rolling mill roll, coated with the mixture (including a continuous roll-to-roll method of processing), doctor blade (" Doctor blade ”), by spraying (“ spray coating ”), by centrifugation, by printing, etc.
- a roller such as a rolling mill roll
- coated with the mixture including a continuous roll-to-roll method of processing
- Doctor blade doctor blade
- spray coating by spray coating
- centrifugation by printing, etc.
- the organic solvent used can be any solvent that does not react with the metal film or the electrode material. Examples include tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), heptane, toluene, or a combination thereof.
- THF tetrahydrofuran
- DMSO dimethyl sulfoxide
- heptane heptane
- toluene or a combination thereof.
- Solid electrode-electrolyte components are also contemplated in this document. These include at least one multilayer material comprising an electrode film, a thin film as described above on the electrode film, and a solid electrolyte film on the thin film.
- the solid electrolyte includes at least one solvating polymer and a lithium salt.
- the electrolyte solvating polymer can be chosen from linear or branched polyether polymers (for example, PEO, PPO, or EO / PO copolymer), poly (dimethylsiloxanes), poly (alkylene carbonates), poly (alkylene sulfones), poly (alkylene sulfonamides), polyurethanes, poly (vinyl alcohol), polyacrylonitriles, polymethyl methacrylates, and their copolymers, the solvating polymer optionally comprising crosslinkable units and optionally being crosslinked.
- the lithium salts that can enter the solid electrolyte are such as those described for the thin film.
- the salt of the solid electrolyte can be chosen from those described above, it can be different or the same as that present in the thin film. It should be noted that this document also contemplates the use of the present electrodes with a gel-type or solid-type polymer electrolyte having properties similar to gel electrolytes.
- the solid electrolyte comprises a ceramic combined or not with a polymer as described in the previous paragraph.
- the electrolyte is a composite comprising a polymer and at least one ceramic, the latter possibly as described for the thin film.
- the solid electrolyte can also include a ceramic without the use of a polymer.
- Such ceramics include, for example, oxide-type ceramics (such as LAGP, LLZO, LATP, etc.), sulfide-type (such as L17P3S11), glass-ceramics, and the like.
- the present technology also relates to electrochemical cells comprising a negative electrode, a positive electrode, and a solid electrolyte, in which at least one of the electrodes is as described in the present application.
- the cell includes the following elements stacked in order:
- the cell includes the following elements stacked in order:
- the cell includes the following elements stacked in order:
- the electrochemical accumulator is a lithium or lithium-ion battery.
- the electrochemical accumulators of the present application are intended for use in nomadic devices, for example mobile phones, cameras, tablets or laptops, in electric or hybrid vehicles, or in the market. renewable energy storage.
- a mixture containing 50% or 70% by mass of Mg2B20s (ceramic sticks), the remainder (50% or 30%) being a mixture of salt (LiTFSI) and crosslinkable polymer based on PEO with an atomic ratio of O: Li 20: 1, is prepared in tetrahydrofuran (THF). The whole is dispersed with a disc mixer (Ultra-Turrax) until a stable suspension is obtained. The quantity of THF is adjusted in order to obtain the adequate viscosity and to be at the limit of causing the ceramic to precipitate at the bottom of the container.
- THF tetrahydrofuran
- dispersions comprising around 20 to 25% by mass of the mixture of “ceramic + polymer + salt + UV crosslinking agent” in the solvent are prepared and spread on a sheet of lithium (pure Li) or of an alloy of Li type. x M y where x> y (for example, alloys of Li and Mg or Al) with a doctor blade or by spraying (by a “spray coater”).
- the lithium or lithium alloy foil is placed in a vacuum glass enclosure or in a chamber filled with an inert gas such as argon (avoid nitrogen, as it reacts quickly with lithium ).
- a UV lamp is lit above the metal film (on the spread layer side) to initiate crosslinking (typically 300 WPI for 5 minutes at 30 cm distance).
- the lithium sheet is then dried at 80 ° C. under vacuum before being used in a battery.
- a thermal crosslinking agent can also be used as a replacement for the UV crosslinking agent.
- the lithium foil is placed under vacuum at 80 ° C at least overnight and is not UV treated.
- Li pure lithium
- LiMg Li and Mg alloy (10% by mass)
- LiAI Li and Al alloy (2000ppm)
- LiFePC (LFP) electrode is made by mixing 73.5% by mass of LFP P2 coated with carbon, 1% by mass of Ketjen carbon TM ECP600, the remainder (25.5%) being a mixture of polymer and LiFSI, is spread on a carbonaceous aluminum collector.
- a mixture of the polymer and LiTFSI (20: 1) without ceramic with a UV initiator in THF is prepared and then spread by the doctor blade method on an LFP cathode. The cathode is then predried for 5 min in an oven at 50 ° C then placed under a UV lamp (300 WPI) for 5 min in an atmosphere nitrogen.
- the polymer used is the same as that used for the thin layer of the metal electrode.
- Figure 1 shows a cross section of a piece of metallic lithium having a thin ceramic layer (E1, 85% AI2O3 spherical). The layer remains intact even during cutting and, although very concentrated in ceramic, it does not crumble.
- Figure 2 shows a thin layer of Mg2B20s ceramic (E4, 50 wt%, 4-5 ⁇ m) on the surface of a LiAl alloy.
- the chemical mapping clearly shows the presence of sulfur (e) and fluorine (f) atoms attributed to the lithium salt, but especially of magnesium (b) atoms coming from the ceramic in the form of very hard rods, which gives a more or less homogeneous surface.
- the nanometric spheres of ALCte sinus, the surface is more homogeneous and one can easily increase the amount of ceramic up to 85% in order to make the progression of dendrites more difficult.
- Figure 3 shows a thin layer of spherical ceramic AI2O3 (85% by mass, 6-7 ⁇ m) on the surface of a LiMg (E2) alloy.
- two layers are clearly visible, one rich in polymer and ceramic, the other very rich in ceramic.
- the top layer is richer in polymer and therefore more tacky to provide very good contact between the lithium therethrough and the solid polymer electrolyte (SPE) which will be hot rolled onto the thin layer.
- SPE solid polymer electrolyte
- Figure 4 shows another example of a thin film, this time with needle-shaped, nanoscale ALCte particles on a LiAI (E5) alloy.
- the polymer very dense agglomerates are obtained and due to the large specific surface of the ceramic only 50% by mass thereof is used. Beyond that, all the polymer is consumed to coat the particles and the film formed on lithium is no longer strong enough to withstand mechanical stress.
- the goal is to find the limit of dissolution of the ceramic in the polymer to form a thin and strong film while being the most concentrated in ceramic to obtain a mixture of the “ceramic polymer” type different from what is usually reported for them. SPEs.
- Figure 5 shows an example of an SPE of about 15-20 ⁇ m directly deposited on a lithium alloy LiAI and composed of spherical ceramic AI2O3 (70% by mass) in the polymer used in Example 1.
- Two layers are clearly visible, one rich in polymer and ceramic, the other very rich in ceramic.
- darker areas making up the polymer are visible in the top image although the majority of this layer is made of ceramic particles (in white).
- SPE will be less effective against dendrites since it is not ceramic dense enough, but will be more sticky to be assembled with another electrode.
- Figure 6 shows another example of SPE (approx. 10-15 ⁇ m) deposited on the surface of lithium alloy LiAI, but this time with 85 wt% AI2O3 spherical ceramic particles in the same polymer. Again, two layers are clearly visible, the first rich in polymer and ceramic, the second very rich in ceramic. Fewer dark areas are visible in the lower layer compared to Figure 5 since it is richer in ceramic. This type of SPE would therefore be more effective against dendrites compared to the example comprising 70% ceramic. However, these last two layers, although thicker, are still not suitable for use as a solid electrolyte since their surface is not tacky enough to adhere to the cathode.
- FIG. 26 shows the thin layer of polymer and salt without ceramic. This layer has a thickness of 4 to 5 ⁇ m.
- Figure 27 shows the chemical mapping of the electrode wafer. The sulfur (f) of the salt and the carbon (e) of the polymer are clearly visible. Electrodes with the thin film comprising the spherical AI2O3 ceramic and the mixture of polymer and lithium salt at different O: Li molar ratios (5: 1, 10: 1, 15: 1, and 20: 1) were also analyzed. .
- Figure 28 shows a thin layer of polymer and salt (O: Li ratio 20: 1) containing 50% by weight of ALCte and measuring about 5 to 5.5 ⁇ m in thickness. The chemical mapping of this same electrode is presented in Figure 29.
- the LFP cathode (LiFePC) is composed of LFP P2 coated with carbon (75.3%), Ketjen TM black (1%), polymer (19.23%), LiTFSI (6.27%).
- the symmetrical Li / SPE / Li cells were also galvanostatically cycled by imposing different constant currents ranging from C / 24 to 1 C. Cyclability tests were also carried out by allowing the battery to cycle in C / 4 until the short circuit. . The impedance measurements on the batteries were made at 50 ° C.
- FIG. 7 shows an SEM image representing the Li / SPE / Li stack after removing a battery which has been cycled and short-circuited. Dendrites are not visible on the slice of the cell analyzed by SEM, but could be present elsewhere in the cell. It should be noted that the aluminum element shown in the chemical mapping comes from the support found behind the sample and not from the sample itself. The measurements of impedance, of cycling stability at a rate of C / 4 and of resistance to various imposed currents were carried out. Four P (a) cells were tested and demonstrated relatively similar impedance curves (see Figure 8 (a)). The interface to load transfer seems inefficient and the semi-arcs are larger.
- Figure 9 (a) shows the spectroscopic impedance measurements made at 50 ° C for 4 symmetrical P (b) cells assembled with standard LiAI alloys. Two of these same cells were studied in cycling stability at a speed of C / 4 ( Figure 9 (b)) and two others in resistance test at different imposed currents ( Figure 9 (c), speed capacity).
- Figure 10 shows the same tests as for Figure 9 except that LiMg alloys were used. The interface to the transfer of charge seems less efficient then the semi-arcs of a circle are larger. Just like for the alloy LiAI, batteries die after about 150 hours under constant current of C / 4 and cannot withstand the application of a current equivalent to C / 6. iv. With unmodified LiAI and SPE with ceramic (Pile (d))
- Lithium modified with a thin layer must be combined with an SPE and a cathode (containing or not itself a thin layer which may be of the same nature). After lamination of the stack at 80 ° C, the contact between the elements is very good and the protective layer rich in ceramic is retained on the lithium side.
- FIG 21 (a) Another test, shown in Figure 21 (a) is to deposit the SPE directly on the lithium (see also Figures 5 and 6). When the thickness is too great, SPE cannot be added and this type of coating is not sticky enough to make good contact with the second unmodified lithium.
- the impedance measurements in Figure 21 (b) show enormous charge transfer resistances due to poor physical contact between the two lithiums and the coating, and to too much ceramic which becomes detrimental in this case. As shown in Figure 21 (c), the batteries cannot be cycled and die prematurely.
- FIG 11 shows a SEM image of a stack after cycling with two lithiums (LiAI) covered with a thin layer of 4 ⁇ m of spherical AI2O3 ceramic (85% by mass).
- LiAI lithiums
- FIG. 11 shows a SEM image of a stack after cycling with two lithiums (LiAI) covered with a thin layer of 4 ⁇ m of spherical AI2O3 ceramic (85% by mass).
- the dendrites are not visible, but the battery P1 presented is after short circuit. Even during cycling, the ceramic layer remains compact, which provides protection to slow the progression of dendrites.
- each ceramic particle small sphere
- Figures 12 (a) to 12 (g) show the SEM image and chemical mapping of stack P1, the latter clearly showing the layer of AI2O3. Locally, the ceramic layer is a little deformed due to the repeated high current cycling to which it has been the object.
- Figure 13 (a) clearly shows that the protected lithium of P1 can cycle without short circuiting up to a rate of 1 C with a low overvoltage.
- Figures 13 (b) and 13 (c) show the spectroscopic impedance measurements made at 50 ° C for 2 symmetrical P1 cells after assembly and after each cycling speed. The impedances are relatively stable during cycling which attests that lithium does not undergo strong deformation even when a strong current is applied.
- Figures 14 (a) and 14 (b) show cycling at 1 C for several cycles of these same P1 cells.
- the two batteries short-circuit between 320-360 hours of cycling which is a clear improvement over the results of the Figure 9.
- the impedances shown in Figures 14 (c) and 14 (d) are stable during high current cycling of 1C (results shown at every three cycles in 1C).
- Figure 15 shows an example of a battery that has cycled and shorted.
- the cell shown is the one whose cycling is shown in Figure 14 (a).
- Figure 14 (a) shows the passage of two dendrite formations.
- Chemical mapping shows that the ALCte layer has been pierced by dendrites and that it is strongly destroyed compared to what can be seen on the SEM images in Figure 12.
- ii With lithium modified by 85% spherical AI2O3 (P2 battery)
- LiAI / SPE / LiAI batteries one side of which is coated with a thin layer of AI2O3 ( needles, 50%) were assembled and cycled. The cycling of the batteries was stopped before short circuit as indicated on the cycling profiles of Figure 18.
- Figure 18 (a) shows the assembly carried out to study the effect of the protective layer on the deformation of lithium, while Figure 18 (b) shows the impedance results of four assembled cells.
- Figure 22 shows that the first two charge / discharge curves are perfect, little polarized and with a very well defined 3.5 V plateau when the Modified LiAI alloys are used ( Figures 22 (b) and (c)). In addition, the results are reproductive. For example, two batteries are shown in Figure 22 (b) and the curves overlap. When lithium LiAI without modification is used, the results are poorly reproducible as can be seen in Figure 22 (a). The discharge capacity is also smaller and the plateau is less well defined for the three batteries.
- FIG. 24 shows the long cycles performed in C / 6 and C / 2 for LFP / SPE / LiMg batteries using unmodified LiMg ( Figure 24 (a)) and that modified with ceramic ( Figure 24 (b)) .
- the cycling is more stable after modification of lithium and particularly of C / 2. Indeed, at this speed, the progression of dendrites is favored and therefore the formation of a short circuit.
- LFP / SPE / Li button cells were assembled as follows:
- Example 1 an LFP cathode as described in Example 1 (d) with a thin ceramic film (50% AI2O3 and O: Li ratio of 10: 1) or without a thin film (reference).
- Figures 30 (a) and 30 (b) respectively show the experiences of long cycling (charge: C / 6, discharge: C / 3) and cycling at different speeds at 80 ° C in button cell batteries.
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US (1) | US20230060872A1 (fr) |
EP (1) | EP4104222A1 (fr) |
JP (1) | JP2023513248A (fr) |
KR (1) | KR20220141832A (fr) |
CN (1) | CN115136359A (fr) |
CA (2) | CA3072784A1 (fr) |
WO (1) | WO2021159209A1 (fr) |
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WO2023133640A1 (fr) * | 2022-01-14 | 2023-07-20 | HYDRO-QUéBEC | Matériau d'électrode avec couche organique, procédés de préparation, et utilisations électrochimiques |
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KR102625654B1 (ko) * | 2021-03-12 | 2024-01-16 | 주식회사 엘지에너지솔루션 | 전극 및 이의 제조방법 |
CA3128220A1 (fr) * | 2021-08-13 | 2023-02-13 | Nicolas DELAPORTE | Electrodes a surface modifiee, procedes de preparation, et utilisations electrochimiques |
CN114516992B (zh) * | 2022-02-07 | 2023-05-12 | 深圳市多合盈新材料有限公司 | 一种抗静电复合气膜材料及其制备方法 |
CN118040074B (zh) * | 2024-04-11 | 2024-07-19 | 蜂巢能源科技股份有限公司 | 一种半固态锂离子电池及其制备方法 |
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2020
- 2020-02-14 CA CA3072784A patent/CA3072784A1/fr not_active Abandoned
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2021
- 2021-02-12 WO PCT/CA2021/050150 patent/WO2021159209A1/fr unknown
- 2021-02-12 JP JP2022548432A patent/JP2023513248A/ja active Pending
- 2021-02-12 US US17/760,011 patent/US20230060872A1/en active Pending
- 2021-02-12 CA CA3166945A patent/CA3166945A1/fr active Pending
- 2021-02-12 CN CN202180014680.0A patent/CN115136359A/zh active Pending
- 2021-02-12 KR KR1020227031219A patent/KR20220141832A/ko unknown
- 2021-02-12 EP EP21753996.4A patent/EP4104222A1/fr active Pending
Non-Patent Citations (3)
Title |
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JUHYE ET AL.: "Dendrite-Free Li Metal Anode for Rechargeable Li-S02 Batteries Employing Surface Modification with a NaAIC14-2S02 Electrolyte", ACS APPL. MATER. INTERFACES, vol. 10, 2018, pages 3 4699 - 34705, XP055847590 * |
PENG ET AL.: "Volumetric variation confinement: surface protective structure for high cyclic stability of lithium metal electrodes", J. MATER. CHEM. A, vol. 4, 2016, pages 24 27 - 2432, XP055847585 * |
WEIJIA ET AL.: "Surface and Interface Modification of Electrode Materials for Lithium-Ion Batteries With Organic Liquid Electrolyte", FRONT. ENERGY RES, 11 September 2020 (2020-09-11), XP055847589, DOI: https://doi.org/10.3389/fenrg.2020.00170 * |
Cited By (1)
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WO2023133640A1 (fr) * | 2022-01-14 | 2023-07-20 | HYDRO-QUéBEC | Matériau d'électrode avec couche organique, procédés de préparation, et utilisations électrochimiques |
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JP2023513248A (ja) | 2023-03-30 |
CN115136359A (zh) | 2022-09-30 |
EP4104222A1 (fr) | 2022-12-21 |
KR20220141832A (ko) | 2022-10-20 |
CA3072784A1 (fr) | 2021-08-14 |
CA3166945A1 (fr) | 2021-08-19 |
US20230060872A1 (en) | 2023-03-02 |
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