CN113972445A - Diaphragm and lithium ion battery containing same - Google Patents
Diaphragm and lithium ion battery containing same Download PDFInfo
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- CN113972445A CN113972445A CN202111143108.2A CN202111143108A CN113972445A CN 113972445 A CN113972445 A CN 113972445A CN 202111143108 A CN202111143108 A CN 202111143108A CN 113972445 A CN113972445 A CN 113972445A
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- lithium ion
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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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
A diaphragm and lithium ion battery containing the diaphragm, at least one of the front and back surfaces of the lithium ion battery diaphragm is coated with a coating layer, the coating layer contains an inorganic material A @ B; the graphene oxide is characterized in that A is an amino acid functionalized graphene quantum dot with the size of 1-20 nm, the number of layers of the graphene quantum dot is less than or equal to 5, and B is a solid electrolyte material; the thickness of the coating layer is 0.5-5.0 um. Due to the introduction of the amino acid functionalized graphene quantum dots, the ionic conductivity of the solid electrolyte material and the mutual compatibility of material interfaces are greatly increased; the lithium ion conductive coating is used as a special coating to be coated on the surface of the diaphragm, so that the lithium ion transmission rate of the diaphragm in the electrochemical process can be greatly improved, and the interface impedance of materials is reduced; the coating layer is strong in stability and good in heat resistance, the thermal stability and the safety performance of the diaphragm are further improved, and the lithium ion battery containing the diaphragm has excellent rate performance, safety and cycle performance.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a diaphragm and a lithium ion battery containing the diaphragm.
Background
Lithium ion secondary batteries are currently widely used in consumer electronics, energy storage systems, and power systems due to high energy density and excellent cycle performance. The diaphragm is used as a key part of the lithium ion battery and mainly plays a role in blocking electrons and enhancing the ion transmission effect. In order to improve the safety performance of a lithium ion battery, a diaphragm safety coating begins to be popularized in a large range in recent years, a main coating layer is boehmite or alumina at present, the heat resistance is mainly achieved, the content of HF (hydrogen fluoride) in an electrolyte is reduced, in addition, aluminum ions have a certain synergistic effect on anode materials of lithium cobaltate, ternary lithium manganate and lithium manganate, and the stability of the materials can be improved. However, the boehmite coating or the alumina coating does not transmit lithium ions and has a certain effect of inhibiting the transmission of the lithium ions to a greater or lesser extent, thereby influencing the rate charge and discharge performance of the battery. Their solid state electrolytes have attracted an extremely great deal of interest to scientists. Therefore, how to improve the ion transmission rate of the safety coating of the diaphragm and ensure the safety function characteristic of the safety coating becomes the focus of research in the field of the diaphragm at present. The invention discovers that the amino acid functionalized graphene quantum dot and solid electrolyte composite system has strong mutual affinity and obvious synergistic effect, and shows extremely excellent ionic conductivity. The material is used for the special coating of the diaphragm, on one hand, the heat-resistant safety characteristic is achieved, on the other hand, the content of HF in electrolyte can be reduced, and the material and the anode material are cooperated with each other; most importantly, the coating layer has extremely high ionic conductivity, so that the charge and discharge rate performance of the lithium ion battery can be greatly improved.
Disclosure of Invention
The invention aims to provide a diaphragm and a lithium ion battery containing the diaphragm, which greatly improve the ionic conductivity and interface compatibility of the diaphragm by introducing a special coating layer, solve the problem of self ionic transmission insulation of the traditional boehmite or alumina coating when being applied to the lithium ion battery, and improve the ionic conduction rate of a positive electrode active material and a negative electrode active material and the interface of the diaphragm, thereby obviously improving the charge-discharge rate characteristic of the lithium ion secondary battery.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a lithium ion battery diaphragm is characterized in that at least one of the front surface and the back surface of the lithium ion battery diaphragm is coated with a coating layer, and the coating layer contains an inorganic material A @ B; the graphene composite material comprises a substrate, a graphene oxide layer and a graphene oxide layer, wherein A is an amino acid functionalized graphene quantum dot, the size of the graphene quantum dot is 1-20 nm, the number of layers of the graphene quantum dot is less than or equal to 5, and B is a pure-phase solid electrolyte material; the thickness of the coating layer is 0.5-5.0um, and the inorganic material A @ B accounts for 50-100% of the mass of the coating layer; in the inorganic material A @ B, the mass ratio of A to B is (0.001-0.0001): 1; the particle size D50 of A @ B is 100-500 nm.
Furthermore, the amino acid functionalized graphene quantum dot contains an amino acid functional group and metal lithium ions.
Further, the amino acid functional group is one or more of glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine, selenocysteine and pyrrolysine.
Further, B is Li1+xAlxTi2-x(PO4)3(0＜x≤1)、LixTiy(PO4)3(0＜x＜2,0＜y＜3)、LiZr2(PO4)3,Li7La3Zr2O12(LLZO)、Li3xLa2/3-xTiO3(LLTO)、Li2ZrCl6、Li10Ge(P1-xSbx)2S12,Li(4-x)Ge(1-x)PxS4(LiGePS), LiPON.
Preferably, the coating layer further contains one or more of water-based PVDF, water-based PMMA, and oil-based PVDF.
The invention also protects a lithium ion battery containing the lithium ion battery diaphragm, which comprises a positive plate, a negative plate, electrolyte and the lithium ion battery diaphragm.
Further, the positive plate comprises a positive active material, and the positive active material contains one or more of lithium iron phosphate, a ternary material, a lithium cobaltate material, a lithium-rich manganese material and a lithium manganate material.
Further, the negative electrode sheet comprises a negative electrode active material, and the negative electrode active material contains one or more of graphite, mesocarbon microbeads, soft carbon, hard carbon, silicon oxide, silicon materials and pre-processed silicon materials.
Further, the electrolyte contains one or more of main solvents EC, PC, DEC, EMC, EA, EP AND PP, one or more of film forming additives VC, VEC, FEC, PS, HTCN, AND AND TMSP, AND functional lithium salt LiPF6、LiBF4、LiFSI、LiODFB、LiPO2F2And one or more of LiTFSI.
Preferably, the thickness of the lithium ion battery diaphragm is 5um-25 um.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a diaphragm and a lithium ion battery containing the diaphragm, wherein the diaphragm contains a special coating layer, so that the lithium ion transmission rate of the diaphragm in the electrochemical process can be greatly improved, and the interface impedance of materials is reduced; in addition, the coating layer is strong in stability and good in heat resistance, the thermal stability and the safety performance of the diaphragm are further improved, and the lithium ion battery prepared by utilizing the diaphragm has excellent rate performance, safety and cycle performance.
In particular, compared with the prior art,
firstly, compared with the traditional diaphragm safety coating, the special coating not only shows the safety characteristic function, but also has excellent ionic conductivity, can improve the ion transmission rate of the diaphragm, and can reduce the transmission impedance of the diaphragm interface;
secondly, amino acid functionalized graphene quantum dots are introduced into the special coating of the diaphragm, the functional groups have strong mutual affinity, the ion conduction is not conductive, and the affinity between the special coating and the interface of a positive electrode material and a negative electrode material is improved;
thirdly, the special coating amino acid functionalized graphene quantum dots of the diaphragm can greatly improve the ionic conductivity of the solid electrolyte, and can reduce polarization and contact impedance for the diaphragm;
fourthly, the diaphragm provided by the invention is applied to a lithium ion battery, has good safety performance, and realizes extremely excellent charge-discharge rate performance and cycle performance.
Drawings
FIG. 1: the cycle life of the battery prepared in the example of the present invention is plotted.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The present embodiment only exemplifies the flexible package battery, but is also applicable to batteries with other outer cases and structures, such as square steel case, cylindrical battery, etc.
Description of typical cell manufacture:
preparing a positive pole piece: adding a positive active material (lithium cobaltate (LCO), Lithium Manganate (LMO), lithium iron phosphate (LFP), a ternary material (NCM)), a polyvinylidene fluoride (PVDF) conductive agent Super-P serving as an adhesive into N-methyl pyrrolidone (NMP) according to a certain mass ratio, stirring and homogenizing to prepare positive slurry, then coating the two sides of the positive slurry on a positive current collector, and drying, compacting, slitting, flaking and welding tabs to obtain the positive pole piece.
Preparing a negative pole piece: adding a negative active material (artificial graphite, silicon alloy, silicon-carbon composite and silicon oxide), an adhesive and a dispersing agent into deionized water according to a required weight ratio, stirring and homogenizing to prepare negative slurry, then coating the two sides of the negative slurry on a negative current collector, and drying, compacting, slitting, sheet-making and welding tabs to obtain a negative pole piece.
Preparing a diaphragm: rolling or spraying the solid electrolyte or the solid electrolyte containing the adhesive (water system or oil system PVDF, water system PMMA) on a base film made of PE or PP material, drying, and cutting into the required diaphragm.
Preparing a lithium ion battery: assembling the negative pole piece and the positive pole piece prepared by the process with a diaphragm, injecting electrolyte to obtain a battery cell, putting the battery cell into an outer package, standing at a high temperature, performing hot-pressing pre-charging, and forming to obtain the lithium ion secondary battery.
The capacity of the lithium ion battery manufactured at this time is 3.5Ah, the charging voltage is 4.45V, and the discharging cut-off voltage is 3.0V.
Example 1:
alanine functionalized graphene quantum dots @ titanium aluminum lithium phosphate Li with D50 being 200nm1.3Al0.3Ti1.7(PO4)3(the mass ratio of the functional graphene quantum dots to the titanium aluminum lithium phosphate is 0.001:1) is coated on one side of a PE diaphragm with the thickness of 9um, and the thickness of the coating layer is 2 um; dispersing lithium cobaltate, conductive carbon black SP and adhesive PVDF in N-methyl pyrrolidone solvent, coating, rolling and slitting to prepare a positive plate; the artificial graphite, the conductive carbon black SP, the binder SBR and the dispersant CMC are dispersed, coated, rolled and cut to prepare a negative plate, and the three are wound (the positive plate corresponds to the special coating layer of the diaphragm) and injected to assemble the lithium ion secondary battery.
Example 2:
performing alanine functionalization on the D50 graphene quantum dots @ titanium aluminum lithium phosphate Li at 200nm1.5Al0.5Ti1.5(PO4)3(the mass ratio of the functional graphene quantum dots to the titanium aluminum lithium phosphate is 0.001:1) and the water system PMMA are coated on one side of the PE diaphragm with the thickness of 9um according to the mass ratio of 95.0:5.0, and the thickness of the coating layer is 2 um; dispersing lithium cobaltate, conductive carbon black SP and adhesive PVDF in N-methyl pyrrolidone solvent, coating, rolling and slitting to prepare a positive plate; dispersing artificial graphite, conductive carbon black SP, a binding agent SBR and a dispersing agent CMC,coating, rolling and slitting to prepare a negative plate, winding the negative plate, the positive plate and the negative plate (the positive plate corresponds to the special coating layer of the diaphragm), injecting liquid and assembling the lithium ion secondary battery.
Example 3:
performing alanine functionalization on the D50 graphene quantum dots @ titanium aluminum lithium phosphate Li at 200nm1.8Al0.8Ti1.2(PO4)3(the mass ratio of the functional graphene quantum dots to the titanium aluminum lithium phosphate is 0.0005:1) and the water system PVDF are coated on one side of a PE diaphragm with the thickness of 9um according to the mass ratio of 90:10, and the thickness of the coating layer is 2 um; dispersing lithium cobaltate, conductive carbon black SP and adhesive PVDF in N-methyl pyrrolidone solvent, coating, rolling and slitting to prepare a positive plate; the artificial graphite, the conductive carbon black SP, the binder SBR and the dispersant CMC are dispersed, coated, rolled and cut to prepare a negative plate, and the three are wound (the positive plate is coated with a special coating layer corresponding to the diaphragm) and injected to assemble the lithium ion secondary battery.
Example 4:
performing alanine functionalization on the D50 graphene quantum dots @ titanium aluminum lithium phosphate Li at 200nm1.8Al0.8Ti1.2(PO4)3(the mass ratio of the functional graphene quantum dots to the titanium aluminum lithium phosphate is 0.0008:1) and the water system PVDF are mixed and coated on one side of the PE diaphragm with the thickness of 9um according to the mass ratio of 80:20, and the thickness of the coating layer is 1.5 um; dispersing lithium cobaltate, conductive carbon black SP and adhesive PVDF in N-methyl pyrrolidone solvent, coating, rolling and slitting to prepare a positive plate; the artificial graphite, the conductive carbon black SP, the binder SBR and the dispersant CMC are dispersed, coated, rolled and cut to prepare a negative plate, and the three are wound (the positive plate is coated with a special coating layer corresponding to the diaphragm) and injected to assemble the lithium ion secondary battery.
Example 5:
performing alanine functionalization on the D50 graphene quantum dots @ titanium aluminum lithium phosphate Li at 200nm1.8Al0.8Ti1.2(PO4)3(the mass ratio of the functional graphene quantum dots to the titanium aluminum lithium phosphate is 0.0001:1) and the oil PVDF are mixed and coated on one side of the PE diaphragm with the thickness of 9um according to the mass ratio of 65:35, and the thickness of the coating layer is 1.5 um; conducting electricity with lithium cobaltateDispersing carbon black SP and a bonding agent PVDF in an N-methyl pyrrolidone solvent, coating, rolling and slitting to prepare a positive plate; the artificial graphite, the conductive carbon black SP, the binder SBR and the dispersant CMC are dispersed, coated, rolled and cut to prepare a negative plate, and the three are wound (the positive plate is coated with a special coating layer corresponding to the diaphragm) and injected to assemble the lithium ion secondary battery.
Example 6:
performing alanine functionalization on the D50 graphene quantum dots @ titanium aluminum lithium phosphate Li at 200nm1.8Al0.8Ti1.2(PO4)3(the mass ratio of the functional graphene quantum dots to the titanium aluminum lithium phosphate is 0.0003:1) and the water system PMMA are coated on the two sides of the PE diaphragm with the thickness of 9um according to the mass ratio of 50:50, and the thickness of the coating layer is 1.5 um; dispersing lithium cobaltate, conductive carbon black SP and adhesive PVDF in N-methyl pyrrolidone solvent, coating, rolling and slitting to prepare a positive plate; the artificial graphite, the conductive carbon black SP, the binder SBR and the dispersant CMC are dispersed, coated, rolled and cut to prepare a negative plate, and the three are wound (the positive plate is coated with a special coating layer corresponding to the diaphragm) and injected to assemble the lithium ion secondary battery.
The test results of the examples illustrate that:
TABLE 1 cell internal resistance and discharge rate Performance in different examples
And (3) analyzing an experimental result:
the above test conditions were all performed at room temperature under standard atmospheric pressure, and table 1 shows the internal resistance and discharge rate performance of different examples, and it can be seen that the batteries prepared in each example exhibited different internal resistances, wherein the internal resistance performance of examples 3 and 6 was superior, and the discharge at high rates of 0.5C, 3.0C and 5.0C exhibited very high capacity retention rate, which is mainly attributed to the improvement of the ionic conductivity of the solid electrolyte by coating the separator. Among them, the lithium ion secondary batteries manufactured in examples 3 and 6 also have a higher voltage plateau energy in the case of 0.2C discharge, and further illustrate the great advantages exhibited by the separator.
TABLE 2 discharge behavior at different temperatures (cut-off 3.0V @0.2C)
Table 2 shows discharge characteristics (cut-off 3.0V @0.2C) at different temperatures, and it can be seen that the battery shows very excellent temperature discharge characteristics by incorporating the separator of the present invention into the battery. At 55 ℃, the discharge capacity retention rate is more than 98%, at 0 ℃, the capacity retention rate can be more than 97%, even at low temperature of-20 ℃, the battery containing the diaphragm also shows the capacity retention rate of more than 92%, compared with the conventional lithium ion battery, the low-temperature performance is greatly improved by 3-5%, and strong performance advantages are shown.
Table 3 charging rate performance data for different examples
Table 3 shows the charging rate performance data of the different examples, it can be seen that the batteries containing the separator show extremely excellent charging performance, the charging constant current ratios are all more than 96% when charged at 0.5C, the charging constant current ratios can be more than 90% when charged at 1.0C, and the batteries containing the separator also show more than 81% even when charged at high 3.0C rate, which is greatly improved compared with the charging performance of the conventional lithium ion batteries.
Fig. 1 is a cycle life curve of 3C charging and 3C discharging at room temperature in example, and it can be seen that example 2 exhibits an ultra-long cycle life, the capacity retention rate is 85% at 1000 cycles, and the main performance difference is attributed to the separator coating layer stability and the overall battery stability in the following examples 6 and 3.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A lithium ion battery separator, characterized in that: coating a coating layer on at least one of the front surface and the back surface of the lithium ion battery diaphragm, wherein the coating layer contains an inorganic material A @ B; the graphene oxide is characterized in that A is an amino acid functionalized graphene quantum dot with the size of 1-20 nm, the number of layers of the graphene quantum dot is less than or equal to 5, and B is a solid electrolyte material; the thickness of the coating layer is 0.5-5.0um, and the inorganic material A @ B accounts for 50-100% of the mass of the coating layer; in the inorganic material A @ B, the mass ratio of A to B is (0.001-0.0001): 1; the particle size D50 of A @ B is 100-500 nm.
2. The lithium ion battery separator according to claim 1, wherein: the amino acid functionalized graphene quantum dot contains an amino acid functional group and metal lithium ions.
3. The lithium ion battery separator according to claim 2, wherein: the amino acid functional group is one or more of glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine, selenium cysteine and pyrrolysine.
4. The lithium ion battery separator according to claim 1, wherein: b is Li1+xAlxTi2-x(PO4)3(0＜x≤1)、LixTiy(PO4)3(0＜x＜2,0＜y＜3)、LiZr2(PO4)3,Li7La3Zr2O12(LLZO)、Li3xLa2/3- xTiO3(LLTO)、Li2ZrCl6、Li10Ge(P1-xSbx)2S12,Li(4-x)Ge(1-x)PxS4(LiGePS), LiPON.
5. The lithium ion battery separator according to claim 1, wherein: the coating layer also contains one or more of water-based PVDF, water-based PMMA or oil-based PVDF.
6. A lithium ion battery comprising the lithium ion battery separator according to any one of claims 1 to 5, wherein: the lithium ion battery diaphragm comprises a positive plate, a negative plate, electrolyte and the lithium ion battery diaphragm.
7. The lithium ion battery of claim 6, wherein: the positive plate comprises a positive active material, and the positive active material contains one or more of lithium iron phosphate, a ternary material, a lithium cobaltate material, a lithium-rich manganese material and a lithium manganate material.
8. The lithium ion battery of claim 6, wherein: the negative plate comprises a negative active material, wherein the negative active material contains one or more of graphite, mesocarbon microbeads, soft carbon, hard carbon, silicon monoxide, silicon materials and pre-processed silicon materials.
9. The lithium ion battery of claim 6, wherein: the electrolyte contains one or more of main solvents EC, PC, DEC, EMC, EA, EP AND PP, one or more of film forming additives VC, VEC, FEC, PS, HTCN, AND AND TMSP, AND functional lithium salt LiPF6、LiBF4、LiFSI、LiODFB、LiPO2F2And one or more of LiTFSI.
10. The lithium ion battery of claim 6, wherein: the thickness of the lithium ion battery diaphragm is between 5um and 25 um.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105742586A (en) * | 2016-02-05 | 2016-07-06 | 江南大学 | Preparation method of graphene quantum dot/nanometer silicon negative electrode material for lithium-ion battery |
| CN109494390A (en) * | 2018-10-30 | 2019-03-19 | 溧阳天目先导电池材料科技有限公司 | A kind of modified solid electrolyte membrane and preparation method thereof and lithium battery |
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2021
- 2021-09-28 CN CN202111143108.2A patent/CN113972445A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105742586A (en) * | 2016-02-05 | 2016-07-06 | 江南大学 | Preparation method of graphene quantum dot/nanometer silicon negative electrode material for lithium-ion battery |
| CN109494390A (en) * | 2018-10-30 | 2019-03-19 | 溧阳天目先导电池材料科技有限公司 | A kind of modified solid electrolyte membrane and preparation method thereof and lithium battery |
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