CN110137561A - Lithium secondary battery additive and the preparation method and application thereof - Google Patents
Lithium secondary battery additive and the preparation method and application thereof Download PDFInfo
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- CN110137561A CN110137561A CN201910354433.XA CN201910354433A CN110137561A CN 110137561 A CN110137561 A CN 110137561A CN 201910354433 A CN201910354433 A CN 201910354433A CN 110137561 A CN110137561 A CN 110137561A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to lithium secondary battery additive technology fields, and in particular to lithium secondary battery additive and the preparation method and application thereof.The additive are as follows: LibMaXc, M B, Al, Ga, In, Y, Sc, Sb, Bi, Nb, Ta, Ti, Zr, V, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Cu, Ag, Zn, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；X is F, Cl, Br or I；0.2≤b≤6；0.1≤a≤3；1≤c≤9.It can improve electrode ion and quickly transmit with high ionic conductivity, air stability, improve electrode load amount, thickness, improve battery energy density.
Description
Technical field
The present invention relates to lithium secondary battery additive technology fields, and in particular to one kind has improvement lithium secondary battery electrode
The additive material and the preparation method and application thereof that ion quickly transmits.
Background technique
When talking about the energy density of battery, lithium secondary battery is an ideal battery system.However, to being at present
Only, the chemical property of lithium secondary battery is still limited by the transmission rate of ion and electronics in electrode layer.It is secondary in lithium
In battery electrode preparation process, the electron propagation ducts of electrode rely primarily on the electronics high conduction materials such as addition conductive carbon and are mentioned
For.On the other hand, the offer of the ion transmission channel of electrode, the lithium secondary battery of organic phase and all solid state lithium secondary battery
Method is different.Since organic bath has high osmosis and wetting capacity, lead in electrode production process
It crosses and reserves the modes such as hole in electrode layer, realize infiltration of the electrolyte in electrode layer and realize biography of the ion in electrode layer
It is defeated.Although this method avoids the addition of additional materials, however, reduction of the presence of a large amount of holes for the energy density of battery
It is also highly significant.Meanwhile this method is difficult to obtain thicker electrode layer, further limits the negative of electrode active material
Carrying capacity.In all-solid-state battery, because solid electrolyte does not have mobility, the infiltration between electrode activity particle and electrolyte
Contact problems are more complicated than liquid phase battery.Therefore, the fast ion material of additional addition is needed applied to the electrode layer of all-solid-state battery
For material to obtain quick ion channel, currently used is all the corresponding solid electrolyte material of addition.However, solid-state is electric at present
Solve problem chemically compatible with electrode material present in matter, the side such as air stability and solvent stability of solid electrolyte
The problem of face and the problems such as solid electrolyte preparation process, make solid electrolyte material be difficult to directly apply to electrode film forming
In technical process.
In view of this, the present invention is specifically proposed.
Summary of the invention
The present invention provides a kind of lithium secondary battery additive, with high ionic conductivity and air stability, energy
Enough improve electrode ion quickly to transmit, improve electrode load amount and thickness, and mutually compatible with existing lithium secondary battery electrode material,
It is expected to solve that the transmission of electrode material ion is relatively slow in lithium secondary battery, electrode material load is low, thickness of electrode is difficult to further mention
The problem of high aspect, to be expected to realize the preparation with high-energy density and the polarized electrode plates of low electrode, into one
Step improves the energy density of lithium secondary battery.Meanwhile the lithium secondary battery additive room temperature ionic conductivity is higher, air is steady
Fixed, preparation method is simple.
Specifically, the present invention provides a kind of lithium secondary battery additive being shown below,
LibMaXc,
Wherein, M is selected from B, Al, Ga, In, Y, Sc, Sb, Bi, Nb, Ta, Ti, Zr, V, Cr, Mo, W, Mn, Tc, Re, Fe, Co,
One or more of Ni, Cu, Ag, Zn, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu；X
Selected from F, Cl, Br, one or more of I；0.2≤b≤6；0.1≤a≤3；1≤c≤9.
In the specific embodiment of the invention, b can be selected from 0.2,0.5,1,2,3,4,5 or 6, it is further preferred that 1≤b
≤3。
In the specific embodiment of the invention, a can be selected from 0.1,0.2,0.5,1,1.5,2,2.5 or 3, further preferably
Ground, 0.2≤a≤1.
In the specific embodiment of the invention, c can be selected from 1,2,3,4,5,6,7,8 or 9, it is further preferred that 3≤c≤
6。
In some preferred embodiments of the present invention, the lithium secondary battery additive is as follows,
Li3Y1-dIndCl6, (glass-ceramic phase)；Wherein, 0≤d≤1；Further, d is selected from 0,0.1,0.2,0.3,
Or 1.0 0.4,0.5,0.6,0.7,0.8,0.9.
Further, lithium secondary battery additive of the present invention can be glass phase, glass-ceramic phase or crystalline phase.
In other preferred embodiments of the invention, the lithium secondary battery additive is as follows,
Li3InCl6(crystalline phase), Li3NbCl8(glass phase), Li3YCl6(glass-ceramic phase).
The above-mentioned lithium secondary battery additive of the present invention can be prepared by this field routine techniques.
Such as it grinds and is made after can mixing according to the ratio required raw material (or predecessor)；Or further using organic molten
Agent is total to molten recrystallization method, heats eutectic method, and the method for making feed particles be in contact in insoluble hydrocarbon organic solvent is made accordingly
The compound of phase.
Further, the raw material (or predecessor) for preparing lithium secondary battery additive of the present invention includes LiX and MXyBefore
Object is driven, wherein the definition of M, X are same as above；1≤y≤6, it is preferable that 2≤y≤5.Such as specifically, y can be selected from 1,2,3,
4,5, or 6.
Specifically, it is described mixing ball can be used, the mode of pearl is mixed, can also under aspheric, the mode of pearl into
Row mixing.It can be mixed, can also be mixed in a manner of without using organic solvent in organic solvent.
Further, the organic solvent can be polar solvent, be also possible to nonpolar solvent.Solvent can dissolve,
It is partly dissolved and does not dissolve above-mentioned LiX and MXyPredecessor.As nonpolar solvent, hydrocarbon solvent and ethers can be enumerated
Solvent.As the hydrocarbon solvent, Aliphatic hydrocarbon solvents and armaticity hydrocarbon solvent can be enumerated.Preferably aliphatic hydrocarbon
Class solvent, further preferably hexane.As the ether solvent, cyclic esters solvent and chain type esters solvent can be enumerated, it is excellent
It is selected as cyclic esters solvent, further preferably tetrahydrofuran.
Further, during preparing lithium secondary battery additive of the present invention, such as in required raw material (or forerunner
Object) NH can be used in mixed process4Cl、I2, the materials such as LiI, S carry out as the ligand of cosolvent, fluxing agent or complex compound
It uses.The advantage is that can reduce reaction temperature, form the acquisition that complex intermediate etc. is conducive to product.
It further, can be by the method for heating anneal by glass phase obtained or glass-ceramic phase in the present invention
Intermediate product is changed into glass-ceramic phase or crystalline phase.
Wherein, the heating anneal temperature is 100-600 DEG C, preferably 150-350 DEG C.The heating anneal time is usually
- 24 hours 10 minutes, preferably 1-10 hours.Heating anneal can carry out in the atmosphere such as air, nitrogen, argon gas, can also be
It is carried out in vacuum atmosphere.
Further, NH can also be added during the heating anneal4Cl、I2, LiI, S, P, the volatile material such as ferrocene
Material carries out the regulation of object phase and pattern.It the advantage is that reduction annealing temperature, while being conducive to improve material ions conductivity.
The invention also includes the lithium secondary battery additives of above method preparation.
The invention also includes the applications that above-mentioned lithium secondary battery additive is used as additive for electrode in the lithium secondary battery, or
Person is preparing the application in lithium secondary battery.Electrode ion transmission speed can be improved using additive of the present invention, and with
Existing lithium secondary battery electrode material is mutually compatible with.
The present invention also provides a kind of lithium secondary battery, at least one of anode layer, electrolyte layer and the negative electrode layers of the battery
Contain one or more kinds of above-mentioned lithium secondary battery additives.
In the present invention, the lithium secondary battery includes liquid phase lithium secondary battery, semisolid and all solid lithium secondary battery.
Lithium secondary battery of the present invention can be prepared by conventional method in that art.
Lithium secondary battery additive provided by the invention can be used as the additive material quickly transmitted with improvement electrode ion
Material.Correspondingly, the material can be applied not only in the lithium secondary battery of organic phase also can be applied to all solid state or semisolid lithium
In secondary cell.The invention has the following advantages that
1. additive for electrode material proposed by the invention is stablized under air conditions, with lithium secondary battery electrode pole piece system
Solvent such as NMP (N-methyl pyrrolones alkane) and adhesive such as PVDF (polyvinylidene fluoride) used in during standby etc. is not sent out
Biochemical reaction.Further, with existing lithium secondary battery electrode material such as sulphur, lithium sulfide, cobalt acid lithium, LiMn2O4, ferric phosphate
The chemistry such as lithium, nickel manganese cobalt acid lithium, high pressure phase nickel ion doped and rich lithium phase manganese base electrode material are mutually compatible.It can be applied directly to
In the technology for preparing electrode of existing maturation.
2. additive for electrode material proposed by the invention has the characteristics that room temperature high ionic conductivity, with active electrode
After material is mixed, quick conduction of the lithium ion between active electrode material and electrolyte can be improved.Therefore, the material
Addition advantageously reduce the interface impedance in electrode slice between active particle and between active particle and electrolyte, to mention
The high rate performance of high lithium secondary battery and the load capacity of active material are further conducive to the energy for improving lithium secondary battery
Density.
3. additive for electrode material proposed by the invention has wider operating temperature and electrochemicaUy inert, electrochemistry
Window will not decompose in battery charge and discharge process up to 6 volts or more.Meanwhile the material preparation method is simple, is easy to secondary in lithium
Use in battery.
Detailed description of the invention
Fig. 1 is glass-ceramic phase Li in embodiment 13Y1-dIndCl6(d=0.2) X-ray diffractogram of additive；
Fig. 2 is glass-ceramic phase Li in embodiment 13Y1-dIndCl6(d=0.2) the alternating temperature ionic conductivity figure of additive；
Fig. 3 is glass-ceramic phase Li in embodiment 13Y1-dIndCl6The value of additive d and corresponding product ion lead variation
Curve.
Fig. 4 is crystalline phase Li in embodiment 23InCl6X-ray diffractogram；
Fig. 5 is crystalline phase Li in embodiment 23InCl6Alternating temperature ionic conductivity figure；
Fig. 6 is LiIn-LiCoO all solid state in application examples 12The charging and discharging curve of secondary cell.
Fig. 7 is the charging and discharging curve of all solid state LiIn-NMC811 secondary cell of application examples 1.
Fig. 8 is the charging and discharging curve of 2 liquid phase Li-LCO secondary cell of application examples.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..It is not specified in embodiment specific
Technology or conditions person, described technology or conditions according to the literature in the art, or carried out according to product description.It is used
Production firm person is not specified in reagent or instrument, is the conventional products that can be commercially available by regular distributor.
In following embodiment, grinding carries out in glove box, hand-ground or machine grinding；Ball milling operation can be in oxygen
Change in zirconium ball grinder and carry out, usually sealing ball milling.
1 glass-ceramic phase Li of embodiment3Y1-dIndCl6Additive and its preparation
30 mMs of LiCl (1.29 grams), 10-10a mMs of InCl3And 10a mMs of YCl3After grinding
It is placed in zirconia ball grinding jar, ratio of grinding media to material 30:1, then sealing ball milling 30 hours, rotational speed of ball-mill is 550 rpms.Ball milling
Gained sample is glass-ceramic phase Li afterwards3Y1-dIndCl6Additive.Wherein, 0 d, 0.1,0.2,0.3,0.4,0.5,0.6,
0.7,0.8,0.9 with 1.0.
Fig. 1, Fig. 2 are respectively glass-ceramic phase Li made from the present embodiment3Y1-dIndCl6(d=0.2) X-ray diffraction
Figure, alternating temperature ionic conductivity figure.Fig. 3 is that the above-mentioned value of d and corresponding product ion lead change curve.
2 crystalline phase Li of embodiment3InCl6Additive and its preparation
30 mMs of LiCl (1.29 grams), 10 mMs of InCl3(2.21 grams) grindings are placed on zirconium oxide ball milling
In tank, ratio of grinding media to material 20:1, then sealing ball milling 20 hours, rotational speed of ball-mill are 550 rpms.Gained intermediate product after ball milling
It is reacted 10 hours for 450 DEG C in sealed silica envelope.Products therefrom is crystalline phase Li3InCl6Additive.
Fig. 4, Fig. 5 are respectively crystalline phase Li made from the present embodiment3InCl6X-ray diffractogram, alternating temperature ionic conductivity
Figure.
3 glass phase Li of embodiment3NbCl8Additive and its preparation
Preparation method is similar to Example 1, and difference is only that: raw materials used as follows: 30 mMs of LiCl (1.29 grams)
With 2.7 grams of NbCl5；Rotational speed of ball-mill is changed to 450 rpms, and Ball-milling Time is 10 hours.Predecessor can obtain after ball milling
Obtain glass phase Li3NbCl8Additive.
4 glass-ceramic phase Li of embodiment3YCl6Additive for electrode material and its preparation
30 mMs of LiCl (1.29 grams), 10 mMs of YCl3(1.95 grams), 20 mMs of ammonium chloride (1.08
Gram) be dissolved in tetrahydrofuran solvent after ground and mixed.Then acquired solution is placed in vacuum oven at 150 DEG C and is dried.Institute
Intermediate product can be obtained glass-ceramic phase Li after 5 hours through calcining 500 DEG C under argon atmosphere3YCl6Additive for electrode material
Material.
The crystalline phase Li of 1 embodiment 2 of application examples preparation3InCl6Additive for electrode material is in all solid state LiIn-LiCoO2、
LiIn-LiNi0.8Mn 0.1Co0.1O2(LiIn-NMC811) application in
Using not modified LiCoO2And NMC811 is positive electrode.With positive electrode: crystalline phase Li3InCl6Electrode
Additive material is that the proportion of 70:30 (mass ratio) is mixed, and mixed process carries out in glove box, and specific process is to adopt
With mortar grinder 20 minutes.Material after grinding is as positive pole powder.Using metal foil indium sheet as cathode, electrolyte is equally used
The Li of business10GeP2S12Electrolyte.Take 100 milligrams of Li10GeP2S12It is 0.785 that electrolyte, which is put into cross-sectional area,
In the mold battery liner of square centimeter, tabletting is carried out with the pressure of 200 megapascal and obtains electrolyte layer.Then, in electrolyte layer
10 milligrams of positive pole powder is added on one side, second of tabletting is carried out with the pressure of 350 megapascal after spreading, anode lamination and electrolysis
Matter is laminated to one piece.Then indium sheet is put into as negative electrode layer in another side.After the completion of whole process, liner is put into mold battery
In, it compresses and tightens screw and be sealed.It can be obtained all solid state LiIn-LiCoO after sealing2With LiIn-NMC811 bis- times
Battery.Wherein all solid state LiIn-LiCoO2Battery carries out charge-discharge test, blanking voltage using 100 microamperes of current density
For 1.9-3.6 volt.The charging and discharging curve figure that Fig. 6 encloses for the 1-5 of the battery, first circle charging capacity every gram of cobalt acid lithium of 142 milliampere hour,
First circle discharge capacity is every gram of cobalt acid lithium of 131 milliampere hour, and corresponding first circle coulombic efficiency is 91.7%.Subsequent battery capacity is stablized
In 130 every gram of cobalt acid lithiums of milliampere hour or so, the invertibity of circulating battery is preferable.Wherein all solid state LiIn-NMC811 battery is adopted
Charge-discharge test is carried out with 100 microamperes of current densities, blanking voltage is 1.9-3.9 volt.Fig. 7 is the charge and discharge of the first circle of the battery
Electric curve graph, first circle charging capacity every gram of NMC811 of 231 milliampere hour, first circle discharge capacity is every gram of NMC811 of 192 milliampere hour, right
The first circle coulombic efficiency answered is 83.1%.
The crystalline phase Li of 2 embodiment 2 of application examples preparation3InCl6Additive for electrode material is in liquid phase Li-LiCoO2In answer
With
Using not modified LiCoO2For positive electrode.With positive electrode: crystalline phase Li3InCl6Additive for electrode material
Proportion for 90:10 (mass ratio) is mixed, and mixed process carries out in glove box, and specific process is using mortar grinder
20 minutes.Material after grinding is as positive pole powder.Using 85wt% positive pole powder, 10wt%PVDF adhesive and 5wt%
Conductive black is stirred slurrying, and the solvent of slurrying uses NMP.Obtained slurry is coated on metal aluminum foil.Through 100 DEG C of vacuum
Drying can be obtained positive plate.Pole piece thickness is greater than 400 microns, and the load of single side LCO is every square centimeter higher than 20 milligrams.With lithium
Piece is to electrode, and polyolefin porous membrane (Celgard 2500) is diaphragm, with LiPF6Ethylene carbonate (EC) and carbonic acid diformazan
For the mixed solution of ester (DMC) (volume ratio 1:1) as electrolyte, CR2016 battery assembly is complete in the glove box of argon atmosphere
At.Electric performance test is carried out at being 25 DEG C in test temperature.Fig. 8 is the charging and discharging curve figure of the first circle of the battery, first circle charging
Capacity every gram of LCO of 139 milliampere hour, first circle discharge capacity are every gram of LCO of 129 milliampere hour, and corresponding first circle coulombic efficiency is
92.8%.
The experimental results showed that, the present invention, which provides lithium secondary battery additive, can improve electrode ion transmission speed above,
And it is mutually compatible with existing lithium secondary battery electrode material.The material room temperature ionic conductivity is higher, air-stable, while the side of preparation
Method is simple, and mutually compatible with existing lithium secondary battery electrode material.It is expected to solve electrode material ion transmission in lithium secondary battery
It is relatively slow, electrode material load is low, the problem of thickness of electrode is difficult to further increase etc., to be expected to realize that there is high-energy
The preparation of density and the polarized electrode plates of low electrode, further increases the energy density of lithium secondary battery.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of lithium secondary battery additive being shown below,
LibMaXc,
Wherein, M is selected from B, Al, Ga, In, Y, Sc, Sb, Bi, Nb, Ta, Ti, Zr, V, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni,
One or more of Cu, Ag, Zn, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu；X choosing
From F, Cl, Br, one or more of I；0.2≤b≤6；0.1≤a≤3；1≤c≤9.
2. lithium secondary battery additive according to claim 1, which is characterized in that
1≤b≤3；And/or
0.2≤a≤1；And/or
3≤c≤6；
Preferably, the lithium secondary battery additive is as follows shown in any formula,
Li3Y1-dIndCl6, wherein 0≤d≤1；Further, d is selected from 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,
0.9 or 1.0；
Li3InCl6Or Li3NbCl8Or Li3YCl6。
3. lithium secondary battery additive according to claim 1 or 2, which is characterized in that the lithium secondary battery additive
For glass phase, glass-ceramic phase or crystalline phase.
4. the preparation method of any one of the claim 1-3 lithium secondary battery additive, which is characterized in that
It grinds and is made after required raw material or predecessor are mixed according to the ratio；Or molten recrystallization is further total to using organic solvent
Method, heats eutectic method, and the compound of corresponding phase is made in the method for making feed particles be in contact in insoluble hydrocarbon organic solvent.
5. the preparation method according to claim 4, which is characterized in that the raw material or predecessor include LiX and MXyForerunner
Object, wherein the definition of M, X are identical as any one of claim 1-3；1≤y≤6, it is preferable that 2≤y≤5.
6. preparation method according to claim 4 or 5, which is characterized in that in the mixed process of required raw material or predecessor
In also add the ligand of appropriate cosolvent, fluxing agent or complex compound, specifically include NH4Cl、I2, LiI or S.
7. according to the described in any item preparation methods of claim 4-6, which is characterized in that the method by heating anneal will be obtained
The glass phase or glass-ceramic phase intermediate product obtained is changed into glass-ceramic phase or crystalline phase；
Wherein, the heating anneal temperature is preferably 100-600 DEG C, and more preferable 150-350 DEG C；The heating anneal time is preferred
It is -24 hours 10 minutes, it is 1-10 hours more preferable；
It is further preferred that being additionally added NH during the heating anneal4Cl、I2, LiI, S, P or ferrocene carry out object phase and shape
The regulation of looks.
8. the lithium secondary battery additive of any one of claim 4-7 the method preparation.
9. any one of claim 1-3,8 the lithium secondary battery additive are used as answering for additive for electrode in the lithium secondary battery
With, or preparing the application in lithium secondary battery；
Wherein, the lithium secondary battery preferably includes liquid phase lithium secondary battery, semisolid and all solid lithium secondary battery.
10. a kind of lithium secondary battery, which is characterized in that at least one of anode layer, electrolyte layer and negative electrode layer of the battery contain
Have: one or more kinds of claim 1-3,8 described in any item lithium secondary battery additives；
Wherein, the lithium secondary battery preferably includes liquid phase lithium secondary battery, semisolid and all solid lithium secondary battery.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910354433.XA CN110137561A (en) | 2019-04-29 | 2019-04-29 | Lithium secondary battery additive and the preparation method and application thereof |
| JP2021564642A JP7390692B2 (en) | 2019-04-29 | 2019-12-19 | Lithium secondary battery solid electrolyte materials, electrodes and batteries |
| US17/607,849 US20220216507A1 (en) | 2019-04-29 | 2019-12-19 | Solid electrolyte material for lithium secondary battery, electrode, and battery |
| EP19926754.3A EP3965199A4 (en) | 2019-04-29 | 2019-12-19 | Solid electrolyte material for lithium secondary battery, electrode, and battery |
| PCT/CN2019/126451 WO2020220697A1 (en) | 2019-04-29 | 2019-12-19 | Solid electrolyte material for lithium secondary battery, electrode, and battery |
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