CN113707837A - Lithium ion solid-state battery anode, preparation process thereof and lithium ion solid-state battery - Google Patents
Lithium ion solid-state battery anode, preparation process thereof and lithium ion solid-state battery Download PDFInfo
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- CN113707837A CN113707837A CN202110021629.4A CN202110021629A CN113707837A CN 113707837 A CN113707837 A CN 113707837A CN 202110021629 A CN202110021629 A CN 202110021629A CN 113707837 A CN113707837 A CN 113707837A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 101
- 238000000576 coating method Methods 0.000 claims abstract description 88
- 239000011248 coating agent Substances 0.000 claims abstract description 84
- 239000007787 solid Substances 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000006255 coating slurry Substances 0.000 claims abstract description 11
- 238000003825 pressing Methods 0.000 claims abstract description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 32
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 30
- 239000001099 ammonium carbonate Substances 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 26
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 15
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 13
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 18
- 239000010410 layer Substances 0.000 description 27
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 239000002203 sulfidic glass Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000010416 ion conductor Substances 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000002001 electrolyte material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229910019208 La0.51Li0.34TiO0.74 Inorganic materials 0.000 description 1
- 229910004043 Li(Ni0.5Mn1.5)O4 Inorganic materials 0.000 description 1
- 229910009294 Li2S-B2S3 Inorganic materials 0.000 description 1
- 229910009292 Li2S-GeS2 Inorganic materials 0.000 description 1
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 description 1
- 229910009298 Li2S-P2S5-Li2O Inorganic materials 0.000 description 1
- 229910009305 Li2S-P2S5-Li2O-LiI Inorganic materials 0.000 description 1
- 229910009304 Li2S-P2S5-LiI Inorganic materials 0.000 description 1
- 229910009311 Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910009324 Li2S-SiS2-Li3PO4 Inorganic materials 0.000 description 1
- 229910009320 Li2S-SiS2-LiBr Inorganic materials 0.000 description 1
- 229910009316 Li2S-SiS2-LiCl Inorganic materials 0.000 description 1
- 229910009318 Li2S-SiS2-LiI Inorganic materials 0.000 description 1
- 229910009313 Li2S-SiS2-LixMOy Inorganic materials 0.000 description 1
- 229910009328 Li2S-SiS2—Li3PO4 Inorganic materials 0.000 description 1
- 229910007560 Li2SiO2 Inorganic materials 0.000 description 1
- 229910009346 Li2S—B2S3 Inorganic materials 0.000 description 1
- 229910009351 Li2S—GeS2 Inorganic materials 0.000 description 1
- 229910009176 Li2S—P2 Inorganic materials 0.000 description 1
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 description 1
- 229910009224 Li2S—P2S5-LiI Inorganic materials 0.000 description 1
- 229910009219 Li2S—P2S5—Li2O Inorganic materials 0.000 description 1
- 229910009222 Li2S—P2S5—Li2O—LiI Inorganic materials 0.000 description 1
- 229910009240 Li2S—P2S5—LiI Inorganic materials 0.000 description 1
- 229910009433 Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910007284 Li2S—SiS2-LixMOy Inorganic materials 0.000 description 1
- 229910007281 Li2S—SiS2—B2S3LiI Inorganic materials 0.000 description 1
- 229910007295 Li2S—SiS2—Li3PO4 Inorganic materials 0.000 description 1
- 229910007291 Li2S—SiS2—LiBr Inorganic materials 0.000 description 1
- 229910007288 Li2S—SiS2—LiCl Inorganic materials 0.000 description 1
- 229910007289 Li2S—SiS2—LiI Inorganic materials 0.000 description 1
- 229910007296 Li2S—SiS2—LixMOy Inorganic materials 0.000 description 1
- 229910007306 Li2S—SiS2—P2S5LiI Inorganic materials 0.000 description 1
- 229910010476 Li4Ti5O4 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 1
- 229910003327 LiNbO3 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013084 LiNiPO4 Inorganic materials 0.000 description 1
- 229910012305 LiPON Inorganic materials 0.000 description 1
- 229910012981 LiVO2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- WVDJDYHWHDLSAZ-UHFFFAOYSA-N [O].[Ti].[La].[Li] Chemical compound [O].[Ti].[La].[Li] WVDJDYHWHDLSAZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- 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
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- 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
-
- H—ELECTRICITY
- 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
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0433—Molding
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a lithium ion solid-state battery anode, a preparation process thereof and a lithium ion solid-state battery. The preparation process of the lithium ion solid-state battery anode comprises the following steps: s1, coating a positive active material layer on the surface of a positive current collector, and drying; s2, coating solid electrolyte coating slurry on the surface of the positive electrode active material layer, wherein the solid electrolyte coating slurry comprises a substance which is solid at normal temperature and forms gas at the temperature of 60-200 ℃; s3, heating and drying at the temperature of 60-200 ℃ to obtain the solid electrolyte coating; and applying pressure to the surface of the positive current collector forming the solid electrolyte coating while heating to compact the surface of the positive current collector to obtain the positive electrode of the lithium ion solid-state battery. The solid electrolyte coating of the anode of the lithium ion solid-state battery has moderate solid content, and the solid electrolyte coating has good stability and uniformity, so that the prepared lithium ion solid-state battery has good capacity retention rate.
Description
Technical Field
The invention belongs to the field of lithium ion solid-state batteries, particularly relates to a lithium ion solid-state battery anode and a preparation process thereof, and particularly relates to a lithium ion solid-state battery prepared from the lithium ion solid-state battery anode.
Background
The all-solid-state lithium ion battery generally comprises three parts, namely a positive electrode, a negative electrode and a solid electrolyte, wherein the positive electrode comprises a positive electrode active material, a binder and a conductive agent; the negative electrode includes a negative electrode active material, a binder, a conductive agent, or uses lithium metal as a negative electrode; the solid electrolyte comprises a binder and an electrolyte material selected from oxide or sulfide solid electrolytes.
In the prior art, it is advantageous to coat a solid electrolyte layer on the surface of the electrode active material layer, and the thinner thickness of the coating layer is more beneficial to improving the performance of the battery, and the solid electrolyte layer comprises a binder and an electrolyte material, and the electrolyte material is selected from oxide or sulfide solid electrolyte. The composition of the solid electrolyte coating layer may be the same as or different from that of the solid electrolyte, and is not particularly limited. However, due to the limitation of the current coating technology, the stability of the coating layer is affected due to the excessively thin coating layer, meanwhile, in the coating process, the excessively high solid content is not beneficial to reducing the thickness of the coating layer, the excessively low solid content is not beneficial to the stability of the coating layer, and the uniformity of the coating layer is ensured.
CN110400905A discloses a pole piece containing solid electrolyte, which comprises a pole piece body and a solid electrolyte coating coated on one side surface or two side surfaces of the pole piece body, wherein the thickness of the solid electrolyte coating is 5-20 μm; the solid electrolyte coating comprises the following raw materials, by weight, 0.5-2 parts of a dispersing agent, 10-40 parts of a solid electrolyte, 1-5 parts of a binder, 50-100 parts of a solvent A, and 50-100 parts of a solvent B; the surface of the pole piece is very smooth, a diaphragm which needs to be arranged in the traditional battery is omitted, and the performance of the pole piece is superior to that of the traditional battery. However, the control of the thickness of the coating layer is difficult to grasp when the solid electrolyte coating is applied, thereby affecting the stability and uniformity of the coating layer.
Therefore, it is very advantageous to find a suitable solid electrolyte coating and coating method for the preparation of lithium ion solid state batteries with good electrical properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a lithium ion solid-state battery anode, a preparation process thereof and a lithium ion solid-state battery.
One of the objectives of the present invention is to provide a process for preparing a positive electrode of a lithium ion solid-state battery, and to achieve the objective, the present invention adopts the following technical scheme:
a preparation process of a lithium ion solid-state battery anode comprises an anode active material layer which comprises an anode active material,
the preparation process of the lithium ion solid-state battery anode comprises the following steps:
s1, coating a positive active material layer on the surface of a positive current collector, and drying;
s2, coating solid electrolyte coating slurry on the surface of the positive electrode active material layer, wherein the solid electrolyte coating slurry comprises a substance which is solid at normal temperature and forms gas at the temperature of 60-200 ℃;
s3, heating and drying at 60-200 ℃ to enable substances which are solid at normal temperature and form gas at 60-200 ℃ in the solid electrolyte coating slurry to be decomposed or volatilized to form gas, and obtaining the solid electrolyte coating; pressing the surface of the positive current collector with the solid electrolyte coating while heating to compact the surface of the positive current collector to obtain the positive electrode of the lithium ion solid-state battery;
wherein the substance which is solid at normal temperature and forms gas at 60-200 ℃ is any one or a mixture of at least two of ammonium bicarbonate, ammonium carbonate and aluminum chloride;
the mass percentage of the substances which are solid at normal temperature and form gas at the temperature of 60-200 ℃ accounts for 5-40% of the total mass of the formula system;
the porosity of the solid state electrolyte coating is < 3%;
the solvent is a non-aqueous solvent.
The solid substance which is easy to decompose and sublimate at low temperature is introduced into the solid electrolyte coating, so that the solid content of the solid electrolyte coating in the coating process is improved, the requirement on coating equipment is reduced, the cost is saved, and meanwhile, in the subsequent process, the solid substance which is easy to decompose and sublimate at low temperature can be decomposed to generate gas or sublimate, so that the thickness of the coating is obviously thinned after the solvent is discharged by drying.
Wherein the mass percentage of the substances which are solid at normal temperature and form gas at 60-200 ℃ accounts for 5-40% of the total mass of the formula system.
Preferably, when the substance which is solid at normal temperature and forms gas at 60-200 ℃ is ammonium bicarbonate, the mass percentage of the ammonium bicarbonate is 15-40% of the total mass of the formula system, for example, the mass percentage of the ammonium bicarbonate is 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40% of the total mass of the formula system.
Preferably, when the substance which is solid at normal temperature and forms gas at 60-200 ℃ is ammonium carbonate, the mass percentage of the ammonium carbonate is 20-30% of the total mass of the formula system, for example, the mass percentage of the ammonium carbonate is 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% of the total mass of the formula system.
Preferably, when the substance which is solid at normal temperature and forms gas at 60-200 ℃ is aluminum chloride, the mass percentage of the aluminum chloride is 5-30% of the total mass of the formula system, for example, the mass percentage of the aluminum chloride is 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% of the total mass of the formula system.
The solid electrolyte coating has a porosity of <3%, preferably a porosity of <1.5%, e.g. the solid electrolyte coating has a porosity of 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9% etc.
The thickness of the solid electrolyte coating is 5 to 30 μm, for example, the thickness of the solid electrolyte coating is 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, and the like.
Preferably, the solid electrolyte coating further comprises a solid electrolyte material and a binder.
Binders include, but are not limited to, polyvinylidene fluoride and/or polytetrafluoroethylene. The solid electrolyte coating may also include PEO. For the solid electrolyte material, it may be a fast ion conductor or other known solid electrolyte material. Fast ionic conductors, also known as lithium ion conducting materials, generally refer to materials with better ion transport properties. The fast ion conductor may be organic or inorganic, including but not limited to LiNbO3、Li4Ti5O4、Li3PO4And LiTFSI, and the like.
Known solid electrolyte materials include any of oxide solid electrolytes, sulfide solid electrolytes, selenide solid electrolytes, and polymer solid electrolytes.
The oxide solid electrolyte is an oxide solid electrolyte, and specifically, LiPON (lithium oxynitride phosphate) and Li can be exemplified1.3Al0.3Ti0.7(PO4)3、La0.51Li0.34TiO0.74、Li3PO4、Li2SiO2And Li2SiO4Any one of lithium lanthanum zirconium oxygen or lithium lanthanum titanium oxygen.
The polymer electrolyte of the present invention generally contains a metal salt and a polymer. In the case where the metal battery according to the present invention is a lithium battery, a lithium salt may be used as the metal salt. As the lithium salt, at least any one of an inorganic lithium salt and an organic lithium salt may be used. The polymer is not particularly limited as long as it forms a complex with a lithium salt, and examples thereof include polyethylene oxide and the like.
As the sulfide solid electrolyte, for example, Li is cited2S-P2S5、Li2S-P2S5-LiI、Li2S-P2S5-Li2O、Li2S-P2S5-Li2O-LiI、Li2S-SiS2、Li2S-SiS2-LiI、Li2S-SiS2-LiBr、Li2S-SiS2-LiCl、Li2S-SiS2-B2S3-LiI、Li2S-SiS2-P2S5-LiI、Li2S-B2S3、Li2S-P2S5-ZmSn、Li2S－GeS2、Li2S－SiS2－Li3PO4Or Li2S－SiS2－LixMOyWherein M and n are positive numbers, Z is any one of Ge, Zn and Ga, x and y are positive numbers, and M is any one of P, Si, Ge, B, Al, Ga and In. Here, the above Li2S-P2S5The description of (A) means that Li is contained2S and P2S5The same applies to the other descriptions of the sulfide solid electrolyte material formed from the raw material composition of (1).
The sulfide solid electrolyte material may contain lithium halide in addition to the above-described ion conductor. Examples of the lithium halide include LiF, LiCl, LiBr, and LiI, and among them, LiCl, LiBr, and LiI are preferable. The ratio of LiX (X ═ F, I, Cl, Br) in the sulfide solid electrolyte material is, for example, in the range of 5mol% to 30mol%, and may be in the range of 15mol% to 25 mol%.
Examples of the solid electrolyte used in the present invention include, in addition to the above, Li2Ti(PO4)3-AlPO4(Ohara glass) and the like.
Preferably, an oxide solid electrolyte is used herein.
The composition of the active material layer of the positive electrode for a lithium ion solid state battery of the present invention is not particularly limited.
For example, for the positive electrode active material layer, the positive electrode active material includes, but is not limited to, LiCoO2、LiMnO2、LiNiO2、LiVO2Ternary materials NMC and LiMn2O4、Li(Ni0.5Mn1.5)O4、LiFePO4、LiMnPO4、LiNiPO4And LiCoPO4And the like. Binders include, but are not limited to, polyvinylidene fluoride PVDF, polytetrafluoroethylene PTFE, styrene butadiene rubber SBR, styrene butadiene rubber, and the like. The conductive agent includes, but is not limited to, acetylene black, ketjen black, super-P, carbon fiber, and the like.
Ammonium carbonate and ammonium bicarbonate form water during decomposition, so that the temperature must be higher than 60 ℃ during heating, so that the water generated by the reaction is completely volatilized, and when the two substances are used, the thickness of the coating cannot be too thick, otherwise, the water inside the coating is difficult to volatilize due to the resistance inside the coating, and the performance of the battery is affected. The sublimation temperature of aluminum chloride is slightly higher and time is required for volatilization, so that a longer residence time needs to be provided in the heating zone.
In step S3, the retention time of heating for ammonium bicarbonate and ammonium carbonate is 2-10 min, such as 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, etc., only the moisture is required to be completely volatilized, and the temperature is preferably 100-115 ℃, such as 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, etc.; the temperature is too high, the retention time is too long, the binder is easy to age, and the performance of the battery is influenced; for aluminum chloride, the temperature is preferably 185-200 ℃, for example 185 ℃, 186 ℃, 187 ℃, 188 ℃, 189 ℃, 190 ℃, 191 ℃, 192 ℃, 193 ℃, 194 ℃, 195 ℃, 196 ℃, 197 ℃, 198 ℃, 199 ℃, 200 ℃ and the like, the retention time is 15-30 min, for example, the retention time is 15min, 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min, 30min and the like, and the aluminum chloride is ensured to be completely volatilized.
In step S3, compacting the surface of the positive electrode current collector on which the solid electrolyte coating is formed while heating; specifically, when the heating area is heated, the double-sided roller structure is used for applying pressure to the surface of an anode current collector such as an aluminum foil for compaction, the applied pressure can ensure that gas generated in the reaction and sublimation processes is exhausted, and on the other hand, the generated gas can be prevented from damaging the microstructure of the solid electrolyte coating, so that the density of the solid electrolyte coating is further improved.
As a preferable scheme of the invention, the preparation process of the lithium ion solid-state battery anode comprises the following steps:
s1, coating a positive active material layer on the surface of a positive current collector, and drying;
s2, coating solid electrolyte coating slurry on the surface of the positive electrode active material layer, wherein the solid electrolyte coating slurry comprises a substance which is solid at normal temperature and forms gas at the temperature of 60-200 ℃;
s3, heating and drying at 60-200 ℃ to enable substances which are solid at normal temperature and form gas at 60-200 ℃ in the solid electrolyte coating slurry to be decomposed or volatilized to form gas, and obtaining the solid electrolyte coating; pressing the surface of the positive current collector with the solid electrolyte coating while heating to compact the surface of the positive current collector to obtain the positive electrode of the lithium ion solid-state battery;
wherein the substance which is solid at normal temperature and forms gas at 60-200 ℃ is any one or a mixture of at least two of ammonium bicarbonate, ammonium carbonate and aluminum chloride;
the porosity of the solid electrolyte coating is less than or equal to 0.5 percent, for example, the porosity of the solid electrolyte coating is 0.1 percent, 0.2 percent, 0.3 percent, 0.4 percent, 0.5 percent and the like.
The lithium ion solid-state battery further comprises a negative electrode, and a solid electrolyte is arranged on the outer side of the solid electrolyte coating.
The composition of the solid electrolyte is different from the solid electrolyte coating.
The thickness of the solid electrolyte is 10 to 300 μm, for example, the thickness of the solid electrolyte is 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, 210 μm, 220 μm, 230 μm, 240 μm, 250 μm, 260 μm, 270 μm, 280 μm, 290 μm, 300 μm, etc.
The invention also aims to provide a preparation process of the lithium ion solid-state battery, which comprises the following steps:
A) preparation of positive pole piece
The positive electrode of the lithium ion solid-state battery prepared by the preparation process of one of the purposes is used as a positive electrode piece;
B) and laminating the prepared positive pole piece, the lithium metal negative pole piece and the lithium lanthanum zirconium oxygen-based solid electrolyte, and assembling to obtain the lithium ion solid battery.
Compared with the prior art, the invention has the beneficial effects that:
the solid content of the solid electrolyte coating of the lithium ion solid-state battery anode is moderate, and the solid electrolyte coating has good stability and uniformity, so that the prepared lithium ion solid-state battery has good capacity retention rate, the first efficiency is 91-94%, the 50-turn capacity retention rate is 91.6-94.6%, and the 100-turn capacity retention rate is 82.2-86.8%.
The preparation process of the lithium ion solid-state battery anode reduces the requirement on coating equipment and saves the cost.
Drawings
FIG. 1 is an SEM photograph of example 1 of the present invention coated with a solid electrolyte layer;
FIG. 2 is an SEM photograph of example 2 of the present invention coated with a solid electrolyte layer;
FIG. 3 is an SEM photograph of example 3 of the present invention coated with a solid electrolyte layer;
fig. 4 is an SEM image of comparative example 1 of the present invention coated with a solid electrolyte layer.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached figures 1-4.
Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.
Example 1
The preparation method of the lithium ion solid-state battery positive electrode of the embodiment is as follows:
1) coating a positive active material layer consisting of 10wt% of PTFE, 10wt% of carbon fiber and 80wt% of nickel cobalt lithium manganate on the surface of the aluminum foil, and drying;
2) dissolving 30wt% of ammonium bicarbonate, 60wt% of lithium lanthanum zirconium oxide and 10wt% of PTFE in NMP (slurry solid content is 60 wt%) to prepare a solid electrolyte coating solution, setting the coating thickness of a coating machine to be 15 mu m, and the conveying speed of an aluminum foil to be 2m/s, and coating the solid electrolyte coating solution on the surface of the positive electrode active material layer;
3) and (3) after coating, the coated electrode plate enters a heating area, the drying temperature is 110 ℃, the retention time is 5min, the electrode plate is dried in an oven at 105 ℃ for 24h after being wound, the dried electrode plate is rolled and cut, and the anode of the lithium ion solid-state battery is obtained, wherein the porosity of the solid electrolyte coating is 1.8%.
The prepared lithium ion solid-state battery anode is used as an anode plate for preparing the lithium ion solid-state battery, and the specific process comprises the following steps:
A) preparation of positive pole piece
The positive electrode of the lithium ion solid-state battery prepared by the preparation method is used as a positive pole piece;
B) and (3) laminating the prepared positive pole piece, the lithium metal negative pole piece and the lithium lanthanum zirconium oxygen-based solid electrolyte, and assembling to obtain the solid lithium ion battery.
Example 2
The preparation method of the lithium ion solid-state battery positive electrode of the embodiment is as follows:
1) coating a positive active material layer consisting of 10wt% of PTFE, 10wt% of carbon fiber and 80wt% of nickel cobalt lithium manganate on the surface of the aluminum foil, and drying;
2) dissolving 30wt% of ammonium carbonate, 60wt% of lithium lanthanum zirconium oxide and 10wt% of PTFE in NMP (slurry solid content is 60 wt%) to prepare a solid electrolyte coating solution, setting the coating thickness of a coating machine to be 15 mu m and the conveying speed of aluminum foil to be 2m/s, and coating the solid electrolyte coating solution on the surface of the positive electrode active material layer;
3) and (3) after coating, the coated electrode plate enters a heating area, the drying temperature is 105 ℃, the retention time is 5min, the electrode plate is dried in an oven at 105 ℃ for 24h after being wound, the dried electrode plate is rolled and cut, and the anode of the lithium ion solid-state battery is obtained, wherein the porosity of the solid electrolyte coating is 1.6%.
The prepared lithium ion solid-state battery anode is used as an anode plate for preparing the lithium ion solid-state battery, and the specific process comprises the following steps:
A) preparation of positive pole piece
The positive electrode of the lithium ion solid-state battery prepared by the preparation method is used as a positive pole piece;
B) and (3) laminating the prepared positive pole piece, the lithium metal negative pole piece and the lithium lanthanum zirconium oxygen-based solid electrolyte, and assembling to obtain the solid lithium ion battery.
Example 3
The preparation method of the lithium ion solid-state battery positive electrode of the embodiment is as follows:
1) coating a positive active material layer consisting of 10wt% of PTFE, 10wt% of carbon fiber and 80wt% of nickel cobalt lithium manganate on the surface of the aluminum foil, and drying;
2) dissolving 30wt% of aluminum chloride, 60wt% of lithium lanthanum zirconium oxide and 10wt% of PTFE in NMP (slurry solid content is 60 wt%) to prepare a solid electrolyte coating solution, setting the coating thickness of a coating machine to be 15 mu m, and the conveying speed of an aluminum foil to be 2m/s, and coating the solid electrolyte coating solution on the surface of the positive electrode active material layer;
3) and (3) after coating, the coated electrode plate enters a heating area, the drying temperature is 195 ℃, the retention time is 20min, the electrode plate is dried in an oven at 105 ℃ for 24h after being wound, the dried electrode plate is rolled and cut, and the anode of the lithium ion solid-state battery is obtained, wherein the porosity of the solid electrolyte coating is 1.5%.
The prepared lithium ion solid-state battery anode is used as an anode plate for preparing the lithium ion solid-state battery, and the specific process comprises the following steps:
A) preparation of positive pole piece
The positive electrode of the lithium ion solid-state battery prepared by the preparation method is used as a positive pole piece;
B) and (3) laminating the prepared positive pole piece, the lithium metal negative pole piece and the lithium lanthanum zirconium oxygen-based solid electrolyte, and assembling to obtain the solid lithium ion battery.
Example 4
Compared with the example 1, the difference is that the heating process is simultaneously carried out with rolling, the rolling thickness is set to be 90% of the thickness of the composite pole piece obtained in the example 1 when the composite pole piece leaves the heating area, and the porosity of the solid electrolyte coating is 0.3%.
Comparative example 1
The comparative example is different from example 1 in that in step 2), a solid electrolyte coating solution was prepared by dissolving 80wt% of lithium lanthanum zirconium oxide and 20wt% of PTFE in NMP, the coating thickness was set to 15 μm and the aluminum foil transfer rate was set to 2m/s by a coater, and the solid electrolyte coating solution was applied to the surface of the positive electrode active material layer.
The thicknesses of the solid electrolyte coatings prepared in the examples 1 to 4 and the comparative example 1 are measured, the experimental results are shown in table 1, the capacity retention rates of the lithium ion solid-state batteries prepared by using the prepared lithium ion solid-state battery anodes as the anodes are measured, and the experimental results are shown in table 2, wherein the testing method comprises the steps of carrying out charge and discharge tests on the batteries obtained in the examples and the comparative example at the temperature of 25 +/-2 ℃, respectively testing the primary efficiency, the capacity retention rate of 50 circles and the capacity retention rate of 100 circles, wherein the charge and discharge voltage is 2.75-4.25V, and the current density is 0.1C.
Fig. 1 is an SEM image of example 1 coated with a solid electrolyte layer, fig. 2 is an SEM image of example 2 coated with a solid electrolyte layer, fig. 3 is an SEM image of example 3 coated with a solid electrolyte layer, fig. 4 is an SEM image of comparative example 1 coated with a solid electrolyte layer, and it can be seen from fig. 1 to 4 that the surface of the positive electrode is more uniform after adding ammonium bicarbonate, ammonium carbonate, and aluminum chloride.
TABLE 1
| Coating thickness (μm) | Thickness (μm) of region heated from the outside | |
| Example 1 | 15.0 | 13.1 |
| Example 2 | 15.0 | 12.6 |
| Example 3 | 15.0 | 11.8 |
| Example 4 | 15.0 | 10.4 |
| Comparative example 1 | 15.0 | 14.8 |
As can be seen from table 1, ammonium bicarbonate, ammonium carbonate and aluminum chloride are completely converted into gas when heated, and thus, the thickness reduction effect is good, and in example 4, rolling is performed simultaneously during the heating process, so that a thinner solid electrolyte layer is obtained. Ammonium carbonate and ammonium bicarbonate form water during decomposition, so that the temperature must be higher than 60 ℃ during heating, so that the water generated by the reaction is completely volatilized, and when the two substances are used, the thickness of the coating cannot be too thick, otherwise, the water inside the coating is difficult to volatilize due to the resistance inside the coating, and the performance of the battery is affected. The sublimation temperature of aluminum chloride is slightly higher and time is required for volatilization, so that a longer residence time needs to be provided in the heating zone.
TABLE 2
| First efficiency (%) | 50-cycle capacity retention (%) | Capacity retention rate at 100 cycles (%) | |
| Example 1 | 92 | 91.6 | 82.2 |
| Example 2 | 91 | 92.8 | 83.1 |
| Example 3 | 93 | 93.3 | 85.6 |
| Example 4 | 94 | 94.6 | 86.8 |
| Comparative example 1 | 90 | 89.2 | 78.6 |
As can be seen from the data in table 2, compared with the solid electrolyte layer in comparative example 1 in which a substance which is solid at room temperature and forms gas at 60 to 200 ℃ is not added, the positive electrode of the lithium ion solid state battery prepared in examples 1 to 3 of the present invention, which is used as the positive electrode plate for the lithium ion solid state battery, can significantly improve the first efficiency and the capacity retention rate of the battery; in example 4, the first efficiency and capacity retention rate of the battery can be further improved by performing the roll pressing simultaneously during the heating process.
The present invention is illustrated by the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, i.e. it is not meant to imply that the present invention must rely on the above-mentioned detailed process equipment and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation process of a positive electrode of a lithium ion solid-state battery, wherein the positive electrode of the lithium ion solid-state battery comprises a positive active material layer, is characterized by comprising the following steps:
s1, coating a positive active material layer on the surface of a positive current collector, and drying;
s2, coating solid electrolyte coating slurry on the surface of the positive electrode active material layer, wherein the solid electrolyte coating slurry comprises a substance which is solid at normal temperature and forms gas at the temperature of 60-200 ℃;
s3, heating and drying at 60-200 ℃ to enable substances which are solid at normal temperature and form gas at 60-200 ℃ in the solid electrolyte coating slurry to be decomposed or volatilized to form gas, and obtaining the solid electrolyte coating; pressing the surface of the positive current collector with the solid electrolyte coating while heating to compact the surface of the positive current collector to obtain the positive electrode of the lithium ion solid-state battery;
wherein the substance which is solid at normal temperature and forms gas at 60-200 ℃ is any one or a mixture of at least two of ammonium bicarbonate, ammonium carbonate and aluminum chloride;
the mass percentage of the substances which are solid at normal temperature and form gas at the temperature of 60-200 ℃ accounts for 5-40% of the total mass of the formula system;
the porosity of the solid electrolyte coating is less than or equal to 0.5 percent
The solvent is a non-aqueous solvent.
2. The preparation process according to claim 1, wherein when the substance which is solid at normal temperature and forms gas at 60-200 ℃ is ammonium bicarbonate, the mass percentage of the ammonium bicarbonate is 15-40% of the total mass of the formula system.
3. The preparation process according to claim 1, wherein when the substance which is solid at normal temperature and forms gas at 60-200 ℃ is ammonium carbonate, the mass percentage of the ammonium carbonate is 20-30% of the total mass of the formula system.
4. The preparation process according to claim 1, wherein when the substance which is solid at room temperature and forms gas at 60-200 ℃ is aluminum chloride, the aluminum chloride accounts for 5-30% of the total mass of the formula system by mass.
5. The production process according to claim 1 or 2, wherein the thickness of the solid electrolyte coating is 5 to 30 μm.
6. The process according to claim 1, wherein in step S3, the heating temperature is 100-115 ℃ and the heating residence time is 2-10 min for ammonium bicarbonate and ammonium carbonate.
7. The process according to claim 1, wherein in step S3, the heating temperature is 185-200 ℃ and the heating residence time is 15-30 min for aluminum chloride.
8. The production process according to claim 1, wherein a solid electrolyte is further provided on the outer side of the solid electrolyte coating, and the composition of the solid electrolyte is different from that of the solid electrolyte coating.
9. The process according to claim 8, wherein the solid electrolyte has a thickness of 10 to 300 μm.
10. A preparation process of a lithium ion solid-state battery is characterized by comprising the following steps:
A) preparation of positive pole piece
The positive electrode of the lithium ion solid-state battery prepared by the preparation process of any one of claims 1 to 9 is used as a positive electrode piece;
B) and laminating the prepared positive pole piece, the lithium metal negative pole piece and the lithium lanthanum zirconium oxygen-based solid electrolyte, and assembling to obtain the lithium ion solid battery.
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