CN110600799A - Method for improving ion conductivity of solid electrolyte of lithium battery - Google Patents

Method for improving ion conductivity of solid electrolyte of lithium battery Download PDF

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Publication number
CN110600799A
CN110600799A CN201910827762.1A CN201910827762A CN110600799A CN 110600799 A CN110600799 A CN 110600799A CN 201910827762 A CN201910827762 A CN 201910827762A CN 110600799 A CN110600799 A CN 110600799A
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solid electrolyte
ionic conductivity
vacuum
increasing
millimeter
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廖健淞
陈庆
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Chengdu New Keli Chemical Science Co Ltd
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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
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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

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  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • Conductive Materials (AREA)
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Abstract

The invention relates to a method for improving the ionic conductivity of a solid electrolyte of a lithium battery, belonging to the field of modification of lithium batteries. In the invention, Li2S，P2S5And stannous bromide are mixed and ball-milled and granulated in a ball mill by using corundum balls to prepare micron-sized particles, the particles are pressed into millimeter-sized sheets and then are sintered for 2-6 hours in vacuum at 180-220 ℃ under the protection of argon, finally, the sintered products are annealed in a vacuum furnace at 230-260 ℃, and finally, the required solid electrolyte is obtained through subsequent treatments such as washing, drying and the like. The invention provides lithium ion vacancy and forms solid solution by doping stannous bromide, and simultaneously melts and fills the gap to inhibit Li2S‑P2S5The material generates impurity phase in the preparation process, thereby improving the conductivity of the solid electrolyte.

Description

Method for improving ion conductivity of solid electrolyte of lithium battery
Technical Field
The invention relates to a method for improving the ionic conductivity of a solid electrolyte of a lithium battery, belonging to the field of modification of lithium batteries.
Background
The lithium ion battery has high energy density, strong stability, no memory effect and long cycle life, and is widely applied as a commercial high-efficiency energy storage device. The electrolyte used in the traditional lithium ion battery is liquid lithium hexafluorophosphate, and the electrolyte is extremely unstable, is easy to decompose to cause battery flatulence, and is extremely easy to combust and explode at high temperature, short circuit, overcharge or physical collision. Despite the protection mechanism added by the external encapsulation, it still has a large safety hazard.
The solid lithium ion battery uses the solid electrolyte to replace the liquid electrolyte, and can fundamentally solve the problem of safe Li of the liquid lithium ion battery2S-P2S5The solid electrolyte theoretically has higher lithium ion conductivity and can achieve liquid electrolysis10 of a mass-2Horizontal, however, during the synthesis, since Li is very easily present during the reaction4P2S6、Li4P2S7Isocratic phases, which reduce the ionic conductivity of the material. Therefore, it is of great practical significance to improve the conductivity of the electrolyte by suppressing the generation of a hetero phase by performing doping modification in the synthesis process.
Chinese patent application No. 201610757259.X discloses a lithium ion conducting sulfide-based solid electrolyte and an all-solid battery using the same. The present invention relates to a lithium ion conductive sulfide-based solid electrolyte and an all-solid-state battery using the same. Disclosed is a lithium ion-conducting sulfide-based solid electrolyte comprising nickel sulfide, and therefore, the solid electrolyte can obtain a novel structure and performance. More specifically, the sulfide-based solid electrolyte contains lithium sulfide (Li) in a specific ratio in mol%2S), phosphorus pentasulfide (P)2S5) And nickel sulfide (Ni)3S2) And exhibits a novel crystal structure due to nickel (Ni). Therefore, the sulfide-based solid electrolyte has greater lithium ion conductivity and a stable crystal structure than conventional sulfide-based solid electrolytes.
Chinese patent application No. 201610653199.7 discloses an oxygen-doped lithium ion solid electrolyte and a method for preparing the same. The invention belongs to the field of lithium ion electrolyte manufacture, and particularly relates to an oxygen-doped lithium ion solid electrolyte and a preparation method thereof, wherein the stoichiometric formula of the lithium ion solid electrolyte is Li10MP2S12-xOxWherein: x is 0.1-0.5, and M is Ge, Si or Sn. Li1 prepared by the invention0MP2S12-xOxLithium ion solid state electrolytes using partial O-substitution of S2-The bond energy of the formed P-O covalent bond is larger than that of the P-S covalent bond, the strengthening of the P-O bond weakens the constraint of oxygen ions on lithium ions, and the migration speed of the lithium ions is improved. So that Li10MP2S12-xThe lithium ion conductivity of the Ox lithium ion solid electrolyte reaches 1.3 multiplied by 10-2S/cm and above.
Application number 201580001316.5Chinese patent discloses a sulfide-based solid electrolyte for lithium ion batteries. The present invention relates to a compound having a cubic thiogenitic crystal structure and consisting of Li7-x- 2yPS6-x-yClxDisclosed is a novel sulfide-based solid electrolyte for a lithium ion battery, which has excellent water resistance and oxidation resistance. A sulfide-based solid electrolyte for a lithium ion battery is provided, which is characterized by containing a compound having a cubic-system thiogenite-type crystal structure and represented by the compositional formula (1): li7-x-2/yPS6-x-yClx, and satisfies 0.8. ltoreq. x.ltoreq.1.7 and 0 in the above composition formula<y≤-0.25x+0.5。
Chinese patent application No. 201580001316.5 discloses a lithium-sulfur system solid electrolyte material for an all solid-state lithium battery and a preparation method thereof. The invention relates to a solid electrolyte material for an all-solid-state lithium battery and a preparation method thereof. The lithium ion battery is characterized in that four different sulfide materials are compounded together according to the molar ratio of Li 2S: A/S: P2S 5: 6: 0.1-4.0: 1.5 to form an amorphous system, so that more effective ways are provided for lithium ion transmission, and higher ion conductivity is obtained. A is Ag, Zn, Al or Zr. With Li2S－ZrS2－P2S5The system is an example, and the room temperature ionic conductivity is about 9.60X 10－6S/cm, 3.30X 10 at 150 DEG C－4S/cm) and lower electron conductivity (room temperature conductivity < 1.0X 10－ 8S/cm, and the material has a wider thermal stability range (room temperature to 200 ℃), thereby providing a more ideal electrolyte candidate material for the practical application of the all-solid-state lithium ion battery.
However, the prepared solid electrolyte has low room temperature conductivity and is difficult to meet the development requirements of solid lithium batteries.
Disclosure of Invention
Against existing Li2S－P2S5The invention relates to the problems that the generation of impure phases is difficult to control and the ionic conductivity is low in the preparation process of a solid electrolyte, and provides a method for improving the ionic conductivity of the solid electrolyte of a lithium battery.
A method for improving the ionic conductivity of a solid electrolyte of a lithium battery comprises the following steps:
a. and (3) granulation: mixing lithium sulfide, phosphorus pentasulfide and stannous bromide according to the weight ratio of 1: 2-6: 0.1-0.6 to obtain a mixture, pouring the mixture into a ball mill, and carrying out ball milling by taking corundum balls as a grinding medium, wherein the ball milling time is 0.8-1.5 hours, and the ball milling rotation speed is 550-800 rpm; preparing micron-sized particles with the particle size less than or equal to 10 mu m;
b. tabletting: pressing the micron-sized particles prepared in the step a into millimeter-sized sheets with the thickness of 0.2-1.0 mm;
c. and (3) sintering: b, sintering the millimeter-scale sheet prepared in the step b at 180-220 ℃ for 2-6 hours in vacuum under the protection of argon to prepare a sintered sheet;
d. annealing: and c, annealing the sintered sheet prepared in the step c in a vacuum furnace at 230-260 ℃, and finally, washing, drying and other subsequent treatments to obtain the required solid electrolyte.
The reaction principle of the invention is as follows: making stannous bromide and Li by ball milling composite granulation2S-P2S5Fully mixing, sintering at low temperature and solidifying to obtain partial Sn2+For Li+Doping to form lithium vacancy and simultaneously forming part of LiBr and Li2S-P2S5The phase forms a solid solution, and the lithium ion conductivity of the material is improved. Unreacted SnBr in the annealing process of 230-260 DEG C2Melt filling to Li2S-P2S5In the voids, Li caused by grain boundary voids and excessive grain boundary content is suppressed4P2S6、Li4P2S7Thereby making the prepared solid electrolyte have higher conductivity.
Wherein the lithium sulfide used is white to yellow crystals. The electrolyte has an inverse fluorite structure, is easy to dissolve in water, soluble in ethanol, soluble in acid and insoluble in alkali, and belongs to an electrolyte material in a rechargeable lithium ion battery. The stannous bromide is adopted to utilize Sn2+So that part of Sn is2+For Li+Doping to form lithium vacancies.
The ball mill is widely applied to the fields of metallurgy, mineral products, electric power, building materials, chemical industry and the like, and is the most commonly used crushing equipment. In order to avoid the influence of the grinding medium on the electrolyte, corundum balls are selected as the grinding medium. The corundum balls are alumina ceramic balls, so that the problem of introducing metal impurities is avoided.
In the step a, corundum balls are used as grinding media for ball milling, the ball milling time is 0.8-1.5 hours, and the ball milling rotating speed is 550-800 rpm so as to prepare micron-sized particles with the particle size of less than or equal to 10 microns.
Further, in the step a, the lithium sulfide, the phosphorus pentasulfide and the stannous bromide are mixed according to the weight ratio of 1:4: 0.2.
Further, in the step a, the ball milling time is 1 hour.
Further, in the step a, the rotation speed of the ball mill is 560 rpm.
Furthermore, in the step a, the particle size of the micron-sized particles is less than or equal to 5 μm.
Further, in step c, the millimeter-scale sheet obtained in step b is sintered in vacuum at 200 ℃ under the protection of argon.
Further, in step c, the millimeter-sized sheet is vacuum-sintered for 2 hours.
Further, in step d, the sintered sheet obtained in step c is annealed in a vacuum furnace at 230 ℃.
Further, in the step d, the drying is carried out for 3-10 hours in vacuum at the temperature of 60 ℃ and the vacuum degree of 20-30 Pa.
The invention also provides a solid electrolyte prepared by the method for improving the ionic conductivity of the solid electrolyte of the lithium battery.
Compared with the prior art, the invention has the following beneficial effects:
1. doping of stannous bromide to provide lithium ion vacancies and form solid solutions while melt filling voids to suppress Li2S-P2S5The material generates impurity phase in the preparation process, thereby improving the conductivity of the solid electrolyte.
2. The lithium battery solid electrolyte prepared by the method has the advantages of simple process, low cost and high conductivity.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1 method for improving ion conductivity of solid electrolyte of lithium battery
The method comprises the following steps:
a. and (3) granulation: taking lithium sulfide, phosphorus pentasulfide and stannous bromide according to the weight ratio of 1:4:0.2, mixing the lithium sulfide, the phosphorus pentasulfide and the stannous bromide to obtain a mixture, pouring the mixture into a ball mill, and carrying out ball milling by using corundum balls as a grinding medium, wherein the ball milling time is 1 hour, and the ball milling speed is 560 rpm; preparing micron-sized particles with the particle size less than or equal to 5 mu m;
b. tabletting: pressing the micron-sized particles prepared in the step a into millimeter-sized sheets with the thickness of 0.3 mm;
c. and (3) sintering: b, sintering the millimeter-scale sheet prepared in the step b at 200 ℃ for 2 hours in vacuum under the protection of argon to prepare a sintered sheet;
d. annealing: c, annealing the sintered sheet prepared in the step c in a vacuum furnace at 230 ℃, and finally carrying out subsequent treatment such as ethanol washing, drying and the like to obtain the required solid electrolyte; the drying is vacuum drying for 8h at 60 ℃ and vacuum degree of 25 Pa.
Example 2 method for improving ion conductivity of solid electrolyte of lithium battery
The method comprises the following steps:
a. and (3) granulation: taking lithium sulfide, phosphorus pentasulfide and stannous bromide according to the weight ratio of 1:2:0.1, mixing the lithium sulfide, the phosphorus pentasulfide and the stannous bromide to obtain a mixture, pouring the mixture into a ball mill, and carrying out ball milling by using corundum balls as a grinding medium, wherein the ball milling time is 0.8 hour, and the ball milling speed is 550 rpm; preparing micron-sized particles with the particle size less than or equal to 10 mu m;
b. tabletting: pressing the micron-sized particles prepared in the step a into millimeter-sized sheets with the thickness of 0.3 mm;
c. and (3) sintering: b, sintering the millimeter-scale sheet prepared in the step b at 180 ℃ for 2 hours in vacuum under the protection of argon gas to prepare a sintered sheet;
d. annealing: c, annealing the sintered sheet prepared in the step c in a vacuum furnace at 230 ℃, and finally obtaining the required solid electrolyte through subsequent treatment such as washing, drying and the like; the drying is vacuum drying for 10h at 60 ℃ and a vacuum degree of 20 Pa.
Example 3 method for improving ion conductivity of solid electrolyte of lithium battery
The method comprises the following steps:
a. and (3) granulation: taking lithium sulfide, phosphorus pentasulfide and stannous bromide according to the weight ratio of 1: 6: 0.6, mixing the lithium sulfide, the phosphorus pentasulfide and the stannous bromide to obtain a mixture, pouring the mixture into a ball mill, and carrying out ball milling by using corundum balls as a grinding medium, wherein the ball milling time is 1.5 hours, and the ball milling speed is 800 rpm; preparing micron-sized particles with the particle size less than or equal to 10 mu m;
b. tabletting: pressing the micron-sized particles prepared in the step a into millimeter-sized sheets with the thickness of 0.3 mm;
c. and (3) sintering: b, sintering the millimeter-scale sheet prepared in the step b at 220 ℃ for 6 hours in vacuum under the protection of argon to prepare a sintered sheet;
d. annealing: c, annealing the sintered sheet prepared in the step c in a vacuum furnace at 260 ℃, and finally obtaining the required solid electrolyte through subsequent treatment such as washing, drying and the like; the drying is vacuum drying for 3h at 60 ℃ and vacuum degree of 30 Pa.
Example 4 method for improving ion conductivity of solid electrolyte of lithium battery
The method comprises the following steps:
a. and (3) granulation: taking lithium sulfide, phosphorus pentasulfide and stannous bromide according to the weight ratio of 1:4:0.2, mixing the lithium sulfide, the phosphorus pentasulfide and the stannous bromide to obtain a mixture, pouring the mixture into a ball mill, and carrying out ball milling by using corundum balls as a grinding medium, wherein the ball milling time is 0.8 hour, and the ball milling speed is 550 rpm; preparing micron-sized particles with the particle size less than or equal to 10 mu m;
b. tabletting: pressing the micron-sized particles prepared in the step a into millimeter-sized sheets with the thickness of 0.3 mm;
c. and (3) sintering: b, sintering the millimeter-scale sheet prepared in the step b at 180 ℃ for 2 hours in vacuum under the protection of argon gas to prepare a sintered sheet;
d. annealing: c, annealing the sintered sheet prepared in the step c in a vacuum furnace at 230 ℃, and finally obtaining the required solid electrolyte through subsequent treatment such as washing, drying and the like; the drying is vacuum drying for 5h at 60 ℃ and under the vacuum degree of 24 Pa.
Example 5A method for improving the ionic conductivity of a solid electrolyte for a lithium battery
The method comprises the following steps:
a. and (3) granulation: taking lithium sulfide, phosphorus pentasulfide and stannous bromide according to the weight ratio of 1:4:0.2, mixing the lithium sulfide, the phosphorus pentasulfide and the stannous bromide to obtain a mixture, pouring the mixture into a ball mill, and carrying out ball milling by using corundum balls as a grinding medium, wherein the ball milling time is 0.8-1.5 hours, and the ball milling speed is 550 rpm; preparing micron-sized particles with the particle size less than or equal to 10 mu m;
b. tabletting: pressing the micron-sized particles prepared in the step a into millimeter-sized sheets with the thickness of 0.3 mm;
c. and (3) sintering: b, sintering the millimeter-scale sheet prepared in the step b at 190 ℃ for 2 hours in vacuum under the protection of argon to prepare a sintered sheet;
d. annealing: c, annealing the sintered sheet prepared in the step c in a vacuum furnace at 250 ℃, and finally obtaining the required solid electrolyte through subsequent treatment such as washing, drying and the like; the drying is vacuum drying for 7h at 60 ℃ and a vacuum degree of 28 Pa.
Comparative example 1
a. And (3) granulation: taking lithium sulfide and phosphorus pentasulfide according to the weight ratio of the lithium sulfide to the phosphorus pentasulfide of 1:4, mixing the lithium sulfide and the phosphorus pentasulfide to obtain a mixture, pouring the mixture into a ball mill, and carrying out ball milling by taking corundum balls as a grinding medium, wherein the ball milling time is 1 hour, and the ball milling speed is 560 rpm; preparing micron-sized particles with the particle size less than or equal to 5 mu m;
b. tabletting: pressing the micron-sized particles prepared in the step a into millimeter-sized sheets with the thickness of 0.3 mm;
c. and (3) sintering: b, sintering the millimeter-scale sheet prepared in the step b at 200 ℃ for 2 hours in vacuum under the protection of argon to prepare a sintered sheet;
d. annealing: c, annealing the sintered sheet prepared in the step c in a vacuum furnace at 230 ℃, and finally obtaining the required solid electrolyte through subsequent treatment such as washing, drying and the like; the drying is vacuum drying for 8h at 60 ℃ and vacuum degree of 25 Pa.
Comparative example 1, which does not incorporate stannous bromide, has the effect of increasing the ionic conductivity of the solid electrolyte.
Comparative example 2
a. And (3) granulation: taking lithium sulfide, phosphorus pentasulfide and stannous bromide according to the weight ratio of 1:4:0.2, mixing the lithium sulfide, the phosphorus pentasulfide and the stannous bromide to obtain a mixture, pouring the mixture into a ball mill, and carrying out ball milling by using corundum balls as a grinding medium, wherein the ball milling time is 1 hour, and the ball milling speed is 560 rpm; preparing micron-sized particles with the particle size less than or equal to 5 mu m;
b. tabletting: pressing the micron-sized particles prepared in the step a into millimeter-sized sheets with the thickness of 0.3 mm;
c. and (3) sintering: b, sintering the millimeter-scale sheet prepared in the step b at 200 ℃ for 2 hours in vacuum under the protection of argon to prepare a sintered sheet; finally, the required solid electrolyte is obtained through subsequent treatments such as washing, drying and the like; the drying is vacuum drying for 8h at 60 ℃ and vacuum degree of 25 Pa.
Comparative example 2, which did not perform annealing treatment at 230 ℃, failed to effectively melt and fill the residual unreacted SnBr2 into Li2S-P2S5 voids, resulted in occurrence of Li4P2S6 and Li4P2S7 due to grain boundary voids and excessive grain boundary content, thereby affecting electrical conductivity.
And (3) performance testing:
conductivity: a simulated battery is prepared by taking a stainless steel sheet as a blocking electrode, and an alternating current impedance test is carried out. Conductivity was measured by glove box. The results are shown in Table 1.
TABLE 1
Numbering Conductivity S/cm
Example 1 1.4×10-3
Example 2 1.7×10-3
Example 3 1.2×10-3
Example 4 1.6×10-3
Example 5 1.6×10-3
Comparative example 1 2.8×10-4
Comparative example 2 8.7×10-4

Claims (9)

1. A method for improving the ionic conductivity of a solid electrolyte of a lithium battery is characterized by comprising the following steps:
a. and (3) granulation: mixing lithium sulfide, phosphorus pentasulfide and stannous bromide according to the weight ratio of 1: 2-6: 0.1-0.6 to obtain a mixture, pouring the mixture into a ball mill, and carrying out ball milling by taking corundum balls as a grinding medium, wherein the ball milling time is 0.8-1.5 hours, and the ball milling rotation speed is 550-800 rpm; preparing micron-sized particles with the particle size less than or equal to 10 mu m;
b. tabletting: pressing the micron-sized particles prepared in the step a into millimeter-sized sheets with the thickness of 0.2-1.0 mm;
c. and (3) sintering: b, sintering the millimeter-scale sheet prepared in the step b at 180-220 ℃ for 2-6 hours in vacuum under the protection of argon to prepare a sintered sheet;
d. annealing: and c, annealing the sintered sheet prepared in the step c in a vacuum furnace at 230-260 ℃, and finally washing and drying to obtain the required solid electrolyte.
2. The method of claim 1, wherein the step of increasing the ionic conductivity of the solid electrolyte comprises: in the step a, lithium sulfide, phosphorus pentasulfide and stannous bromide are mixed according to the weight ratio of 1:4: 0.2.
3. The method of claim 1, wherein the step of increasing the ionic conductivity of the solid electrolyte comprises: in the step a, the ball milling time is 1 hour.
4. The method of claim 1, wherein the step of increasing the ionic conductivity of the solid electrolyte comprises: in the step a, the rotation speed of the ball mill is 560 rpm.
5. The method of claim 1, wherein the step of increasing the ionic conductivity of the solid electrolyte comprises: in the step a, the particle size of the micron-sized particles is less than or equal to 5 microns.
6. The method of claim 1, wherein the step of increasing the ionic conductivity of the solid electrolyte comprises: in the step c, the millimeter-scale sheet prepared in the step b is sintered in vacuum at 200 ℃ under the protection of argon.
7. The method of claim 1, wherein the step of increasing the ionic conductivity of the solid electrolyte comprises: in step c, the millimeter-sized sheet is vacuum sintered for 2 hours.
8. The method of claim 1, wherein the step of increasing the ionic conductivity of the solid electrolyte comprises: in step d, the sintered sheet obtained in step c is annealed in a vacuum furnace at 230 ℃.
9. The method of claim 1, wherein the step of increasing the ionic conductivity of the solid electrolyte comprises: in the step d, the drying is carried out for 3-10 hours in vacuum at the temperature of 60 ℃ and the vacuum degree of 20-30 Pa.
CN201910827762.1A 2019-09-03 2019-09-03 Method for improving ion conductivity of solid electrolyte of lithium battery Withdrawn CN110600799A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112002939A (en) * 2020-08-31 2020-11-27 成都新柯力化工科技有限公司 Clean preparation method of lithium battery solid electrolyte

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112002939A (en) * 2020-08-31 2020-11-27 成都新柯力化工科技有限公司 Clean preparation method of lithium battery solid electrolyte
CN112002939B (en) * 2020-08-31 2021-10-15 成都新柯力化工科技有限公司 Clean preparation method of lithium battery solid electrolyte

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