CN112563562A - Method for improving contact between LLZO solid electrolyte and electrode - Google Patents
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- 238000004528 spin coating Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims description 25
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 24
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229920000307 polymer substrate Polymers 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 244000137852 Petrea volubilis Species 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002019 doping agent Substances 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910003480 inorganic solid Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- AEXDMFVPDVVSQJ-UHFFFAOYSA-N trifluoro(trifluoromethylsulfonyl)methane Chemical group FC(F)(F)S(=O)(=O)C(F)(F)F AEXDMFVPDVVSQJ-UHFFFAOYSA-N 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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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
- H01M10/058—Construction or manufacture
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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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
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Abstract
The invention provides a method for improving the contact between a LLZO solid electrolyte and an electrode, which improves the contact by spin coating a polymer electrolyte on the surface of the LLZO electrolyte, and has the advantages that the polymer electrolyte and the LLZO electrolyte only need to be compounded by the spin coating method, and the advantages of good contact between the polymer electrolyte and the electrode and high ion conductivity of the LLZO electrolyte are combined, so that the composite solid electrolyte with low electrode contact resistance and high ion conductivity is obtained. The method has simple steps, is easy for large-scale industrial production, and has good application prospect.
Description
Technical Field
The invention relates to a method for improving contact between a composite solid electrolyte and an electrode, which is applied to the field of manufacturing of all-solid-state lithium ion batteries.
Background
The lithium ion battery has the advantages of high energy density, wide working temperature range, environmental friendliness, large output power, low self-discharge and the like, and is widely applied to the fields of electric automobiles, energy storage equipment, electronic equipment and the like. However, the traditional lithium ion battery contains organic electrolyte which has the characteristics of flammability and easy explosion. If the organic electrolyte leaks under the action of external force, faults such as short circuit and the like are easily caused, and accidents such as combustion, explosion and the like of the battery can be caused in serious cases.
The solid electrolyte is used as a substitute for organic electrolyte, and has the advantages of good chemical stability, long cycle life, high energy density, good mechanical property, stability for lithium metal cathode, simple preparation and assembly and the like. The solid electrolyte comprises an inorganic solid electrolyte, an organic solid electrolyte and a composite electrolyte. Wherein the inorganic solid electrolyte effects the transfer of charge primarily through the movement of lithium ions.
Cubic phase (LLZO) is a material which is researched more in inorganic solid electrolyte and has the advantages of high lithium ion conductivity, good chemical stability, wide electrochemical window and the like. However, the failure to make intimate contact between the LLZO and the electrode results in a large contact resistance between the two. The polymer electrolyte has the characteristics of softness and easy deformation, and can be in relatively close contact with electrode materials.
Disclosure of Invention
In order to improve the situation that the poor contact between the LLZO solid electrolyte and the electrode material causes the overlarge sheet resistance, the invention aims to provide a method for improving the contact between the LLZO solid electrolyte and the electrode.
The purpose of the invention is realized by the following scheme: a method for improving contact between a LLZO solid electrolyte and an electrode by spin-coating a polymer electrolyte on a surface of a LLZO electrolyte sheet, comprising the steps of:
(1) LiOH. H was weighed in terms of atomic ratio Li: La: Zr =7:3:22O、La2O3、ZrO2Wherein, willLa2O3Putting the mixture into a muffle furnace for heating to remove water;
(2) drying the La2O3And LiOH. H2O、ZrO2And alcohol or isopropanol as a dispersing agent is put into a ball milling tank for ball milling, and is dried after the ball milling is finished, so as to obtain mixed powder;
(3) putting the dried mixed powder into a muffle furnace for presintering at 900 ℃, and performing ball milling and drying again after heating;
(4) pressing the powder after the pre-sintering into a wafer by a tablet machine, then placing the wafer into a muffle furnace for sintering at 1200-1260 ℃, and polishing the LLZO solid electrolyte sheet by using sand paper after sintering;
(5) adding a polymer substrate and lithium salt into anhydrous acetonitrile, stirring until the polymer substrate and the lithium salt are dissolved, then coating the solution on a LLZO solid electrolyte sheet through a spin coater, and drying in a vacuum oven;
(6) and (5) repeating the step, coating the solution on the other side of the LLZO solid electrolyte sheet and drying to finish the spin coating of the polymer electrolyte on the two sides of the LLZO electrolyte sheet.
Further, Ga is adopted in the step (1)2O3As a dopant, LiOH. H was weighed in terms of atomic ratio Li: La: Zr: Ga =6.25:3:2:0.252O、La2O3、ZrO2、Ga2O3。
On the basis of the scheme, La is dried in the step (1)2O3The temperature of (1) is 850 ℃ and 950 ℃, and the drying time is 12 hours.
On the basis of the scheme, the rotation speed of ball milling in the steps (2) and (3) is 300rpm, and the ball milling time is 12-18 hours.
Based on the above scheme, in the step (3), the pre-sintering time is 6 hours.
On the basis of the scheme, in the step (4), the sintering time is 12-16 hours.
On the basis of the above scheme, in the step (5), the polymer substrate is polyethylene oxide (PEO), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) or Polyacrylonitrile (PAN), and the lithium salt is bis (trifluoromethyl)Sulfonyl) imide Lithium (LiTFSI), lithium perchlorate (LiClO)4) Lithium bis (oxalato) borate (LiBOB), spin coating speed was 3000 rpm.
The invention provides a method for improving the contact between a LLZO solid electrolyte and an electrode, which comprises the steps of coating a polymer electrolyte on the surface of the LLZO solid electrolyte in a spinning mode, exerting the soft characteristic of the polymer electrolyte, and enabling the polymer electrolyte to spread on the surface of the LLZO, so that a continuous and uniform conductive interface is formed between the LLZO solid electrolyte and the electrode, and the problem that the interface resistance is overlarge due to point contact between the LLZO solid electrolyte and the electrode is solved.
The invention has the advantages that: the method has simple steps, utilizes the soft characteristic of the polymer electrolyte to spread the polymer electrolyte on the surface of the LLZO, thereby forming a continuous and uniform conductive interface between the LLZO solid electrolyte and the electrode and solving the problem of overlarge interface resistance caused by point contact between the LLZO solid electrolyte and the electrode. Is easy for large-scale industrial production and has better application prospect.
Drawings
FIG. 1 is a graph of ion conductivity data at different temperatures for the completed LLZO/PEO solid state composite electrolyte prepared in example 1.
Detailed Description
The present invention is described in detail by the following specific examples, but the scope of the present invention is not limited to these examples.
Example 1
A method for improving the contact between the LLZO solid electrolyte and an electrode, which is realized by spin coating a polymer electrolyte on the surface of a LLZO electrolyte sheet, comprises the following steps:
(1) LiOH. H was weighed in terms of atomic ratio Li: La: Zr =7:3:22O、La2O3、ZrO2Wherein, La is firstly added2O3Putting the mixture into a muffle furnace, and heating the mixture at 850-950 ℃ to remove water for 12 hours;
(2) drying the La2O3And LiOH. H2O、ZrO2And alcohol or isopropanol as dispersant is put into a ball milling tank for ball milling 12 hours, putting the mixture into an oven for drying after the ball milling is finished to obtain mixed powder;
(3) putting the dried mixed powder into a muffle furnace for presintering at 900 ℃ for 6h, and performing ball milling and drying again after heating;
(4) pressing the powder after the pre-sintering into a wafer by a tablet press, then placing the wafer into a muffle furnace to be sintered for 12 hours at 1240 ℃, and polishing the LLZO solid electrolyte sheet by using sand paper after the sintering is finished;
(5) adding polymer substrate PEO and lithium salt LiTFSI into anhydrous acetonitrile, stirring until the solution is dissolved, then coating the solution on a LLZO solid electrolyte sheet through a spin coater, and drying in a vacuum oven;
(6) and (5) repeating the step, coating the solution on the other side of the LLZO solid electrolyte sheet and drying to finish the spin coating of the polymer electrolyte on the two sides of the LLZO electrolyte sheet.
FIG. 1 is a graph of ion conductivity data of the completed LLZO/PEO solid-state composite electrolyte prepared in this example 1 at different temperatures, and it can be seen that the material has higher ion conductivity.
The LLZO solid electrolyte and electrode contact interface impedance of the two-sided spin-coated polymer electrolyte is shown in Table 1 and is 196. omega. cm2。
Example 2
A method for improving the contact between LLZO solid electrolyte and electrode, in which Ga as raw material is increased in step (1) as compared with example 12O3As a dopant, the following steps are carried out:
(1) LiOH. H was weighed in accordance with the atomic ratio Li: La: Zr: Ga =6.25:3:2:0.252O、La2O3、ZrO2、Ga2O3First, La is added2O3Putting the mixture into a muffle furnace, and heating the mixture at 850-950 ℃ to remove water for 12 hours;
(2) drying the La2O3、LiOH·H2O、ZrO2、Ga2O3And alcohol or isopropanol as a dispersing agent are put into a ball milling tank for ball milling for 12 hours, and are put into an oven for drying after the ball milling is finished, so as to obtain mixed powder;
(3) putting the dried mixed powder into a muffle furnace for presintering at 900 ℃ for 6h, and performing ball milling and drying again after heating;
(4) pressing the powder after the pre-sintering into a wafer by a tablet press, then placing the wafer into a muffle furnace for sintering at 1240 ℃ for 12 hours, and polishing the LLZO solid electrolyte sheet by using sand paper after the sintering is finished;
(5) adding polymer substrate PEO and lithium salt LiTFSI into anhydrous acetonitrile, stirring until the solution is dissolved, then coating the solution on a LLZO solid electrolyte sheet through a spin coater, and drying in a vacuum oven;
(6) and (5) repeating the step, coating the solution on the other side of the LLZO solid electrolyte sheet and drying to finish the spin coating of the polymer electrolyte on the two sides of the LLZO electrolyte sheet.
The LLZO solid electrolyte and electrode contact interface impedance of the two-sided spin-coated polymer electrolyte is shown in Table 1 and is 173. omega. cm2。
Example 3
A method for improving the contact between the LLZO solid electrolyte and an electrode, which is realized by spin coating a polymer electrolyte on the surface of a LLZO electrolyte sheet, comprises the following steps:
(1) LiOH. H was weighed in terms of atomic ratio Li: La: Zr =7:3:22O、La2O3、ZrO2Wherein, La is firstly added2O3Putting the mixture into a muffle furnace, and heating the mixture at 850-950 ℃ to remove water for 12 hours;
(2) drying the La2O3And LiOH. H2O、ZrO2And alcohol or isopropanol as a dispersing agent is put into a ball milling tank for ball milling for 12 hours, and is put into an oven for drying after the ball milling is finished, so as to obtain mixed powder;
(3) putting the dried mixed powder into a muffle furnace for presintering at 900 ℃ for 6h, and performing ball milling and drying again after heating;
(4) pressing the powder after the pre-sintering into a wafer by a tablet press, then placing the wafer into a muffle furnace to be sintered for 12 hours at 1240 ℃, and polishing the LLZO solid electrolyte sheet by using sand paper after the sintering is finished;
(5) mixing polymer substrate PEO and lithium salt LiClO4Adding anhydrous acetonitrile and stirring until dissolved, thenCoating the solution on a LLZO solid electrolyte sheet through a spin coater, and drying in a vacuum oven;
(6) and (5) repeating the step, coating the solution on the other side of the LLZO solid electrolyte sheet and drying to finish the spin coating of the polymer electrolyte on the two sides of the LLZO electrolyte sheet.
The interface impedance of the LLZO solid electrolyte and the electrode contact of the two-sided spin-coated polymer electrolyte is shown in Table 1 and is 215. omega. cm2，
Claims (7)
1. A method for improving contact between a LLZO solid electrolyte and an electrode, wherein the contact between the LLZO solid electrolyte and the electrode is improved by spin coating a polymer electrolyte on a surface of a LLZO electrolyte sheet, comprising the steps of:
(1) LiOH. H was weighed in terms of atomic ratio Li: La: Zr =7:3:22O、La2O3、ZrO2. La2O3Putting the mixture into a muffle furnace for heating to remove water;
(2) drying the La2O3And LiOH. H2O、ZrO2And alcohol or isopropanol as a dispersing agent is put into a ball milling tank for ball milling, and is dried after the ball milling is finished, so as to obtain mixed powder;
(3) putting the dried mixed powder into a muffle furnace for presintering at 900 ℃, and performing ball milling and drying again after heating;
(4) pressing the powder after the pre-sintering into a wafer by a tablet machine, then placing the wafer into a muffle furnace for sintering at 1200-1260 ℃, and polishing the LLZO solid electrolyte sheet by using sand paper after sintering;
(5) adding a polymer substrate and lithium salt into anhydrous acetonitrile, stirring until the polymer substrate and the lithium salt are dissolved, then coating the solution on a LLZO solid electrolyte sheet through a spin coater, and drying in a vacuum oven;
(6) and (5) repeating the step, coating the solution on the other side of the LLZO solid electrolyte sheet and drying to finish the spin coating of the polymer electrolyte on the two sides of the LLZO electrolyte sheet.
2. The method for improving LLZO solid state electrolyte and electrode contact according to claim 1 wherein Ga is used in step (1)2O3As a dopant, LiOH. H was weighed in accordance with the atomic ratio Li: La: Zr: Ga =6.25:3:2:0.252O、La2O3、ZrO2、Ga2O3。
3. The method for improving the contact between the LLZO solid electrolyte and the electrode according to claim 1 or 2, wherein the La is dried in the step (1)2O3The temperature of (1) is 850 ℃ and 950 ℃, and the drying time is 12 hours.
4. The method for improving the contact between the LLZO solid electrolyte and the electrode according to claim 1, wherein the ball milling in steps (2) and (3) is performed at a rotational speed of 300rpm for a ball milling time of 12 to 18 hours.
5. The method for improving the contact between the LLZO solid electrolyte and the electrode according to claim 1, wherein the pre-firing time in step (3) is 6 hours.
6. The method for improving LLZO solid state electrolyte and electrode contact according to claim 1 wherein in step (4) the sintering time is 12-16 hours.
7. The method for improving the contact between the LLZO solid electrolyte and the electrode according to claim 1, wherein in the step (5), the polymer substrate is polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene copolymer or polyacrylonitrile, the lithium salt is lithium bis (trifluoromethylsulfonyl) imide, lithium perchlorate or lithium bis (oxalato) borate, and the spin coating speed is 3000 rpm.
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Application publication date: 20210326 |