CN112803064B - Sulfide composite solid electrolyte membrane, preparation method and application - Google Patents
Sulfide composite solid electrolyte membrane, preparation method and application Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 69
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000012528 membrane Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- 239000003792 electrolyte Substances 0.000 claims abstract description 40
- 239000002203 sulfidic glass Substances 0.000 claims abstract description 31
- 230000009477 glass transition Effects 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 18
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- 239000002002 slurry Substances 0.000 claims description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 9
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- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- -1 polyethylene terephthalate Polymers 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011268 mixed slurry Substances 0.000 claims description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 208000027765 speech disease Diseases 0.000 claims 1
- 238000011068 loading method Methods 0.000 abstract description 9
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- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
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- 239000002245 particle Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000010345 tape casting Methods 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 229910003480 inorganic solid Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- VYQRBKCKQCRYEE-UHFFFAOYSA-N ctk1a7239 Chemical compound C12=CC=CC=C2N2CC=CC3=NC=CC1=C32 VYQRBKCKQCRYEE-UHFFFAOYSA-N 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
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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
-
- 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
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of all-solid batteries, in particular to a sulfide composite solid electrolyte membrane, a preparation method and application in all-solid batteries. The electrolyte raw material comprises 80-97 parts by weight of sulfide solid electrolyte and 3-20 parts by weight of low glass transition temperature polymer; wherein the polymer number average molecular weight range is 4000-30000, and the glass transition temperature is-70 to-50 ℃. The sulfide composite solid electrolyte provided by the invention has higher mechanical flexibility due to the adoption of the binder with low glass transition temperature, and the preparation process of the sulfide composite solid electrolyte membrane is simplified. Wherein the solid electrolyte prepared by the method has high ion conductivity (not less than 10) ‑4 ) And the excellent characteristic of matching high-loading capacity positive electrode circulation.
Description
Technical Field
The invention relates to the technical field of all-solid batteries, and relates to a sulfide composite solid electrolyte membrane, a preparation method and application thereof in all-solid batteries.
Background
At present, in a lithium ion battery, an electrolyte mainly adopts an organic electrolyte, so that a great amount of heat generated in other abnormal working states such as overcharge, internal short circuit and the like can cause the rapid vaporization of the electrolyte, further battery explosion and ignition combustion can be caused, and the fundamental solution of the potential safety hazards is to develop a solid-state energy storage device, namely, a non-volatile solid electrolyte is used for replacing the organic electrolyte to develop a solid-state lithium battery technology based on a high-safety solid electrolyte system.
Solid electrolytes are mainly classified into two main categories: inorganic solid electrolytes and polymer solid electrolytes. Although the inorganic solid electrolyte has high conductivity, it has poor solid-solid interface contact with an electrode and has too large interface resistance. The polymer solid electrolyte has strong plasticity, but the applicable temperature range is narrow, and the conductivity is low. It is difficult to satisfy the practical application requirements using a single inorganic solid electrolyte or polymer solid electrolyte.
Based on this, an organic/inorganic composite solid electrolyte membrane has been produced. Sulfide solid electrolytes in inorganic solid electrolytes have high ionic conductivity but have weak processability, and have serious interface problems when contacting with positive and negative electrodes. The Chinese patent application No. CN 111908437A discloses a preparation method of a sulfide electrolyte, but the electrolyte does not have the rapid charge and discharge capacity, so the application scene is limited. The practical application problem can be solved by adding the polymer to the polymer so as to facilitate the practical processing production. If the solid electrolyte can be made thin and can be matched with high-load anode circulation, the method is very important for improving the energy density of the solid battery. Chinese patent application No. CN 109361015 a discloses a sulfide composite electrolyte. The sulfide composite solid electrolyte is prepared from the raw materials for preparing the sulfide solid electrolyte matrix or the poly alkenyl carbonate and the sulfide solid electrolyte matrix. However, the electrolyte cannot be matched to a high loading positive electrode to achieve assembly of a high energy density battery. Therefore, suitable polymers are particularly important for the preparation of organic-inorganic composite electrolytes.
Disclosure of Invention
The invention aims to provide a sulfide composite solid electrolyte membrane, a preparation method and application thereof in an all-solid-state battery.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a sulfide composite solid electrolyte membrane, the electrolyte raw materials are counted according to the weight portion, 80-97 portions of sulfide solid electrolyte, 3-20 portions of low glass transition temperature polymer; wherein the polymer number average molecular weight range is 4000-30000, and the glass transition temperature is-70 to-50 ℃.
The polymer with low glass transition temperature is a copolymer of butadiene and one or more of styrene, acrylonitrile, acrylamide, acrylic acid, tetrafluoroethylene, vinylidene fluoride and tetrafluoroethylene and a derivative thereof;
or
With tertiary amines (R) 3 N) in-situ preparation; or a tertiary amine-containing polymer and a halogenated ether molecule (CR) 2 X-O-CR 3 X ═ F, Cl, Br, I) in situ; or from trimethylene carbonate monomer by polymerization; or trimethylene carbonate monomer and a di-terminal alcohol molecule (HO-R-OH) containing an ether structure.
The above-mentioned
With tertiary amines (R) 3 N) in-situ preparation; or a tertiary amine-containing polymer and a halogenated ether molecule (CR) 2 X-O-CR 3 X ═ F, Cl, Br, I) in situ; or from trimethylene carbonate monomer by polymerization; or trimethylene carbonate monomer and a di-terminal alcohol molecule containing an ether structure (HO-R-OH) are polymerized, preferably, the polymer obtained by the polymerization reaction is represented by the following structural general formula:
in the above-mentioned formula, the compound has the following formula,
a is selected from methyl, cyano, halogen, CF 3 (ii) a R is selected from alkyl with less than eighteen carbon atoms; r is 1 Is selected from NH 2 NHR, OR, hydroxyethyl,
R 2 Selected from halogen, OH, alkyl of ten carbons or less, aryl of eighteen carbons or less, heteroaryl of eighteen carbons or less; r 3 Selected from H, alkyl of ten carbons or less, hydroxyethyl, aryl of eighteen carbons or less, heteroaryl of eighteen carbons or less,
R 4 、R 5 、R 6 Are respectively the same or different and are selected from eight carbons or lessAn alkyl group; z is selected from H or methyl; n is 10-3000; m is selected from 0-2000; p is selected from 0-6; q is 0 to 100.
Preferred low glass transition temperature polymers are copolymers of butadiene and acrylonitrile or polytrimethylene carbonate,
The sulfide solid electrolyte is one or more of LiPSX (X ═ CI, Br, I) solid electrolyte, LiSiPSX (X ═ Cl, Br, I) solid electrolyte, LiGPS solid electrolyte and LiPS solid electrolyte.
A preparation method of a sulfide composite solid electrolyte membrane,
s1, fully grinding the sulfide solid electrolyte;
s2, dissolving the polymer with low glass transition temperature in an organic solvent to prepare a uniform solution containing 3-20 parts by weight of the polymer;
s3, adding 80-97 parts by weight of sulfide solid electrolyte into the uniform solution, and stirring to uniformly disperse the sulfide solid electrolyte to obtain mixed slurry;
s4, uniformly coating the slurry on a substrate, and drying to obtain the sulfide composite electrolyte uniformly distributed on the surface of the substrate;
and S5, separating the composite electrolyte from the matrix to obtain the sulfide composite solid electrolyte membrane.
In step S2, the organic solvent is one or more of toluene, p-xylene, ethyl acetate, isobutyl isobutyrate, acetonitrile.
The substrate described in step S4 is a polyethylene terephthalate film (PET).
In step S4, the slurry is coated on the substrate with a thickness of 20-100um and released from the substrate surface under a pressure of 150-400 MPa.
An all-solid battery comprising the sulfide composite electrolyte.
The sulfide composite electrolyte membrane is transferred to the surface of a pole piece of the lithium electronic battery by a transfer printing method.
The invention has the advantages that:
the sulfide composite solid electrolyte membrane uses the binder with low glass transition temperature, can thin the composite electrolyte, has the characteristic of high ionic conductivity, and can be matched with a high-capacity anode for charge-discharge circulation; the method specifically comprises the following steps:
1. the sulfide composite solid electrolyte membrane provided by the invention adopts the adhesive with low glass transition temperature as the composite material, and the adhesive is directly and uniformly mixed with the sulfide through the solvent, so that the composite electrolyte membrane is obtained, and the preparation process of the composite electrolyte is simplified.
2. The sulfide composite solid electrolyte membrane provided by the invention can be matched with a high-loading positive electrode on the premise of meeting the requirement of thinning the thickness of the sulfide composite solid electrolyte membrane, and the assembly of a high-energy-density solid battery is realized.
Drawings
FIG. 1 is a surface topography of a sulfide composite electrolyte in example 1 of the present invention.
FIG. 2 is an optical photograph of a sulfide composite electrolyte in example 1 of the present invention.
Fig. 3 is a graph of ionic conductivity of a sulfide composite electrolyte at different temperatures in example 2 of the present invention.
Fig. 4 is a graph of charge and discharge capacity at 0.2C at normal temperature in example 2 of the present invention.
Fig. 5 is a graph of charge-discharge specific capacity at 0.2C at room temperature in example 2 of the present invention.
FIG. 6 is a graph of long cycle at 0.2C at room temperature for electrochemistry in example 2 of the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and examples.
The invention discloses a sulfide composite solid electrolyte membrane, which consists of the following raw materials: 80-97 parts of sulfide solid electrolyte, 3-20 parts of low glass transition temperature polymer; the sulfide is used as a main body, and the polymer is used as a filler.
Wherein, the sulfide solid electrolyte needs to be fully ground to obtain the sulfide electrolyte with the particle diameter in the range of 3-20 um;
the sulfide solid electrolyte is one or more of LiPSX (X ═ CI, Br, I) solid electrolyte, LiSiPSX (X ═ CI, Br, I) solid electrolyte, LiGPS solid electrolyte and LiPS solid electrolyte; the invention discloses a preparation method of a sulfide composite solid electrolyte membrane, which mainly comprises the following steps: s1, fully grinding the sulfide solid electrolyte to obtain the electrolyte with the particle diameter of 10-20 um;
s2, dissolving a polymer binder in an organic solvent to prepare a uniform solution containing 3-20 parts by weight of the binder;
s3, adding 80-97 parts of sulfide solid electrolyte into the uniform solution, and stirring to uniformly disperse the sulfide solid electrolyte to obtain mixed slurry;
s4, uniformly coating the slurry on a substrate, and drying to obtain the sulfide composite electrolyte uniformly distributed on the surface of the substrate;
and S5, releasing the composite electrolyte from the matrix under proper pressure.
In conclusion, the obtained sulfide composite solid electrolyte has higher mechanical flexibility due to the adoption of the binder with low glass transition temperature, and the preparation process of the sulfide composite solid electrolyte membrane is simplified. Wherein the solid electrolyte prepared by the method has high ion conductivity (not less than 10) -4 ) And the excellent characteristic of matching high-loading capacity positive electrode circulation.
For a further understanding of the contents, features and effects of the present invention, the following examples are illustrated in the accompanying drawings and described in the following detailed description:
example 1
A sulfide composite solid electrolyte membrane comprises, by weight, 7 parts of a polymer and 93 parts of a LiPSCl sulfide solid electrolyte; the preparation process comprises the following steps: firstly, fully grinding the LiPSCl sulfide solid electrolyte to obtain an electrolyte with a particle diameter within a range of 15 um; the polymer with low glass transition temperature is
(n＝80,m＝10；T g At-60 ℃), number average molecular weight 5000, dissolving the polymer in xylene organic solvent, preparing a homogeneous solution containing 7 parts of polymer; adding 93 parts of LiPSCl sulfide solid electrolyte into the uniform solution, continuously stirring in a centrifuge tube for 24 hours to obtain uniformly dispersed viscous slurry, uniformly distributing the slurry on a PET substrate by adopting a tape-casting coating method, heating on a heating table at 80 ℃ for 24 hours to remove the solvent, and then drying in a vacuum drying oven at 80 ℃ for 24 hours to remove the residual solvent to obtain a sulfide composite solid electrolyte membrane with the thickness of about 70um (see figure 1 and figure 2).
As shown in fig. 1, the prepared composite electrolyte has a scanning electron microscope image, and the sulfide composite solid electrolyte membrane is a composite electrolyte composed of a high content inorganic electrolyte, and the scanning electron microscope image shows that the high content inorganic electrolyte is dispersed relatively uniformly.
As shown in the optical photograph of fig. 2, the prepared sulfide composite electrolyte has excellent flexibility, can be bent, and has good self-supporting property.
Example 2
A sulfide composite solid electrolyte membrane comprises, by weight, 5 parts of a polymer and 95 parts of LiSiPSCl sulfide solid electrolyte; the preparation process comprises the following steps: firstly, fully grinding LiSiPSCl sulfide solid electrolyte to obtain electrolyte with the particle diameter of about 15 um; the polymer with low glass transition temperature is
(n＝100,m＝20；T g At-65 ℃), number average molecular weight 6000, dissolving the polymer in isobutyl isobutyrate organic solvent to prepare a homogeneous solution containing 5 parts of binder; adding 95 parts of sulfide electrolyte into the uniform solution, continuously stirring in a centrifuge tube for 24 hours to obtain uniformly dispersed viscous slurry, uniformly distributing the slurry on a PET substrate by adopting a tape-casting coating method, heating on a heating table at 80 ℃ for 24 hours to remove the solvent, and then drying in a vacuum drying oven at 80 ℃ for 24 hours to remove residual substancesThe remaining solvent was used to obtain a sulfide composite solid electrolyte membrane having a thickness of about 50 um.
And (3) carrying out performance measurement on the obtained sulfide composite solid electrolyte membrane:
NCM622 is used as a positive electrode, and the loading capacity is 34.3mg/cm 2 And taking lithium metal as a negative electrode, and carrying out a charge-discharge test within a test voltage range of 2.6-4.3V.
As shown in FIG. 4, a high loading ternary NCM positive electrode material of 34.3mg/cm is adopted 2 The prepared sulfide composite solid electrolyte can be matched with a high-capacity anode at normal temperature, and the unit area capacity can reach 4.8mAh/cm 2 This performance has reached the positive electrode high loading level of lithium ion batteries assembled using liquid electrolytes.
As shown in FIG. 5, a high-loading ternary NCM cathode material of 34.3mg/cm is adopted 2 The prepared sulfide composite electrolyte can be matched with a high-capacity anode at normal temperature, and the anode can normally exert normal specific capacity of 140 mAh/g.
As shown in FIG. 6, a high-loading ternary NCM cathode material of 34.3mg/cm is adopted 2 The sulfide composite solid electrolyte membrane and the lithium sheet are assembled into a battery, and the battery can stably circulate for 150 circles, and shows good circulation stability.
Example 3
This example is identical to example 1 in all other parameters except that polytrimethylene carbonate is used as the low glass transition temperature polymer, the number average molecular weight is 8000 and the weight ratio of polymer to LPSCl is 95: 5.
Example 4
A sulfide composite solid electrolyte membrane is prepared by the following process steps: firstly, fully grinding the LiPSCl sulfide solid electrolyte to obtain an electrolyte with a particle diameter within a range of 15 um; according to the weight parts, polyepichlorohydrin (Mn is 10000) and triethylamine are mixed according to the weight ratio of 9.52: dissolving in acetonitrile at a ratio of 0.48 to obtain polymer solutionLiquid; adding 90 parts of LiPSCl sulfide solid electrolyte into the uniform solution, continuously stirring the solution in a centrifugal tube for 24 hours to obtain uniformly dispersed viscous slurry, uniformly distributing the slurry on a PET substrate by adopting a tape-casting coating method, heating the PET substrate on a heating table at the temperature of 80 ℃ for 24 hours to remove the solvent, and finishing the polymerization process of polyepichlorohydrin and triethylamine to obtain the polymer
The number average molecular weight was 10000, and then the residual solvent was removed by drying in a vacuum oven at 80 ℃ for 24 hours to obtain a sulfide composite solid electrolyte membrane having a thickness of about 60 um.
Example 5
This example is identical to example 4 in all other parameters, except that the low glass transition temperature polymer used is a copolymer of butadiene and methyl acrylate (mass ratio of butadiene to methyl acrylate 100:1) with a number average molecular weight of 7000, where the ratio of polymer to LPSCl is 92: 8.
Example 6
This example is identical to example 1 in all other parameters, except that the low glass transition temperature polymer used is a copolymer of butadiene with acrylonitrile and butyl acrylate (butadiene with acrylonitrile and butyl acrylate in a 100: 5: 1 mass ratio) with a number average molecular weight of 30000, where the ratio of polymer to LPSCl is 92: 8.
Example 7
This example is identical to example 1 with respect to all other parameters, except that a low glass transition temperature polymer is used which has the structure
(n＝100,m＝20；T g At-65 ℃ C.), a number average molecular weight of 6000, wherein the ratio of polymer to LPSCl is 95: 5.
Example 8
A sulfide composite solid electrolyte membrane is prepared by the following process steps: first, the LiPSCl sulfide solid electrolyte was sufficiently ground to obtain a particle diameterAn electrolyte in the 15um range; based on the parts by weight, the following components are added
(n is 200) and
according to the weight ratio of 12.5: 7.5 in acetonitrile to obtain a polymer solution; adding 80 parts of LiPSCl sulfide solid electrolyte into the uniform solution, continuously stirring in a centrifuge tube for 24 hours to obtain uniformly dispersed viscous slurry, uniformly distributing the slurry on a PET substrate by adopting a tape-casting coating method, heating on a heating table at 80 ℃ for 24 hours to remove the solvent, and heating in the heating process
Completing the in-situ polymerization process to obtain the polymer
The number average molecular weight was 12000, and then the residual solvent was removed by drying in a vacuum oven at 120 ℃ for 24 hours to obtain a sulfide composite solid electrolyte membrane having a thickness of about 70 um.
Example 9
A sulfide composite solid electrolyte membrane is prepared by the following process steps: firstly, fully grinding LiSiPSCl sulfide solid electrolyte to obtain electrolyte with the particle diameter within the range of 25 um; combining trimethylene carbonate with
(m-3) (mass ratio 5:2) in a weight ratio of 10: 4 in acetonitrile to obtain a polymer solution; adding 86 parts of LiSiPSCl sulfide solid electrolyte into the uniform solution, continuously stirring in a centrifuge tube for 24 hours to obtain uniformly dispersed viscous slurry, uniformly distributing the slurry on a PET substrate by adopting a tape-casting coating method, heating on a heating table at the temperature of 80 ℃ for 24 hours to remove the solvent, and preparing the solvent from the uniform solution by using trimethylene carbonate,
The polymerization is completed to obtain a polymer
The number average molecular weight was 8000, and then the residual solvent was removed by drying for 24 hours in a vacuum oven at 80 ℃ to obtain a sulfide composite solid electrolyte membrane having a thickness of about 65 um.
Example 10
This example is identical to example 1 with respect to all other parameters, except that a low glass transition temperature polymer is used which has the structure
(n-40, m-50) and a number average molecular weight of 15000.
The conductivity test was performed on the sulfide composite solid electrolyte membranes prepared in examples 1 to 10, and the test results are shown in table 1.
The test method is as follows:
the conductivity of the sulfide composite solid electrolyte membrane was measured by an ac impedance method. Before measurement, a blocking type battery is assembled in a glove box filled with argon, a sulfide composite solid electrolyte membrane (CSE) is punched into a circular sheet with the diameter of 10mm, and then the circular sheet is clamped between two Stainless Steel (SS) electrodes to assemble a stainless steel/sulfide composite solid electrolyte membrane/stainless (SS/CES/SS) measurement system. An AC impedance spectrum test is carried out by using a biologic-VMP300 electrochemical workstation, and in the test process, the AC perturbation amplitude is set to be 5mV, and the scanning frequency range is 100 KHz-7 MHz. The temperature of the system was measured at 30 ℃. The temperature change test range is 30-80 ℃, and the measurement is carried out once every 10 ℃.
TABLE 1
| Ionic conductivity (S/cm) at 30 DEG C | |
| Example 1 | 2.0ⅹ10 -4 S/cm |
| Example 2 | 2.71ⅹ10 -4 S/cm |
| Example 3 | 2.33ⅹ10 -4 S/cm |
| Example 4 | 3.12ⅹ10 -4 S/cm |
| Example 5 | 1.65ⅹ10 -4 S/cm |
| Example 6 | 2.56ⅹ10 -4 S/cm |
| Example 7 | 2.83ⅹ10 -4 S/cm |
| Example 8 | 1.17ⅹ10 -4 S/cm |
| Example 9 | 3.23ⅹ10 -4 S/cm |
| Example 10 | 3.04ⅹ10 -4 S/cm |
Ionic Electrolysis was performed according to examples 1 to 10The ionic conductivity of the sulfide composite electrolyte membrane prepared from the selected target polymer is higher than 10 in a conductivity test -4 S/cm。
The sulfide composite solid electrolyte of example 1 had an ionic conductivity of 2.0 x 10 at 30 ℃ as measured by a temperature-variable ionic conductivity test (shown in FIG. 3) -4 S/cm。
Therefore, the polymer with low glass transition temperature is adopted as the composite material, and the prepared sulfide composite solid electrolyte can meet the requirement of high ionic conductivity, so that the practical application is realized.
In addition, in examples 1 to 10, in the preparation of the sulfide composite solid electrolyte, the ionic conductivity was still 10 without adding lithium salt -4 And more than S/cm.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A sulfide composite solid electrolyte membrane characterized in that: the electrolyte raw material comprises 80-97 parts by weight of sulfide solid electrolyte and 3-20 parts by weight of low glass transition temperature polymer; wherein the number average molecular weight of the polymer is 5000-30000, and the glass transition temperature is-70 to-60 ℃;
the polymer with low glass transition temperature is a copolymer of butadiene and one or more of styrene, acrylonitrile, acrylamide, acrylic acid, tetrafluoroethylene, vinylidene fluoride and tetrafluoroethylene and a derivative thereof;
or
With tertiary amines R 3 N is prepared in situ; or a polymer containing tertiary amine and a halogenated ether molecule CR 2 X-O-CR 3 Prepared in situ, wherein X = F, Cl, Br, I; or from trimethylene carbonate monomer by polymerization; or trimethylene carbonate monomer and a di-terminal alcohol molecule HO-R-OH containing an ether structure are obtained through polymerization reaction;
wherein: r is selected from alkyl with less than eighteen carbon atoms;
R 2 selected from halogen, OH, alkyl of ten carbons or less, aryl of eighteen carbons or less, heteroaryl of eighteen carbons or less;
R 3 selected from H, alkyl of ten carbons or less, hydroxyethyl, aryl of eighteen carbons or less, heteroaryl of eighteen carbons or less,
；
n is 10-3000; m is selected from 0 to 2000.
2. The sulfide composite solid electrolyte membrane according to claim 1, wherein: the above-mentioned
With tertiary amines R 3 N is prepared in situ; or a polymer containing tertiary amine and a halogenated ether molecule CR 2 X-O-CR 3 Prepared in situ, wherein X = F, Cl, Br, I; or from trimethylene carbonate monomer by polymerization; or the structural general formula of the polymer obtained by polymerizing trimethylene carbonate monomer and a diol molecule HO-R-OH containing an ether structure is shown as follows:
In the above-mentioned formula, the compound of formula,
a is selected from methyl, cyano, halogen, CF 3 R is selected from alkyl with less than eighteen carbon atoms; r 1 Is selected from NH 2 NHR, OR, hydroxyethyl,
、
、
；R 2 Selected from halogen, OH, alkyl of ten carbons or less, aryl of eighteen carbons or less, heteroaryl of eighteen carbons or less; r 3 Selected from H, alkyl with less than ten carbon atoms, hydroxyethyl, aryl with less than eighteen carbon atoms, heteroaryl with less than eighteen carbon atoms,
；R 4 、R 5 、R 6 Each independently are the same or different and are selected from alkyl groups having eight or less carbons; z is selected from H or methyl; n is 10-3000; m is selected from 0-2000; p is selected from 0 to 6; q is 0 to 100.
3. The sulfide composite solid electrolyte membrane according to claim 1, wherein said sulfide solid electrolyte is LiPSX, wherein X = CI, Br, I, lisispsx, wherein X = one or more of Cl, Br, I, lisps, LiPS.
4. A method for producing the sulfide composite solid electrolyte membrane according to claim 1,
s1, fully grinding the sulfide solid electrolyte;
s2, dissolving the polymer with low glass transition temperature in an organic solvent to prepare a uniform solution containing 3-20 parts by weight of the polymer;
s3, adding 80-97 parts by weight of sulfide solid electrolyte into the uniform solution, and stirring to uniformly disperse the sulfide solid electrolyte to obtain mixed slurry;
s4, uniformly coating the slurry on a substrate, and drying to obtain sulfide composite electrolyte uniformly distributed on the surface of the substrate;
and S5, separating the composite electrolyte from the matrix to obtain the sulfide composite solid electrolyte membrane.
5. The method according to claim 4, wherein in step S2, the organic solvent is one or more of toluene, p-xylene, ethyl acetate, isobutyl isobutyrate, and acetonitrile.
6. The production method for a sulfide composite electrolyte membrane according to claim 4, wherein the substrate in step S4 is a polyethylene terephthalate film.
7. The method as claimed in claim 4, wherein the slurry is coated on the substrate to a thickness of 20-100um and is released from the surface of the substrate under a pressure of 150-400MPa in step S4.
8. An all-solid battery comprising the sulfide composite solid electrolyte membrane according to claim 1.
9. The all-solid battery according to claim 8, wherein the sulfide composite solid electrolyte film is transferred to the surface of a pole piece of the lithium electronic battery by a transfer method.
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