CN117691080A - Positive electrode plate and application thereof - Google Patents
Positive electrode plate and application thereof Download PDFInfo
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- CN117691080A CN117691080A CN202311712729.7A CN202311712729A CN117691080A CN 117691080 A CN117691080 A CN 117691080A CN 202311712729 A CN202311712729 A CN 202311712729A CN 117691080 A CN117691080 A CN 117691080A
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- lithium
- solid electrolyte
- electrode active
- layer
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- 239000007784 solid electrolyte Substances 0.000 claims abstract description 89
- 239000010410 layer Substances 0.000 claims abstract description 81
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000011162 core material Substances 0.000 claims abstract description 37
- 239000007774 positive electrode material Substances 0.000 claims abstract description 37
- 239000011247 coating layer Substances 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- 239000010416 ion conductor Substances 0.000 claims description 19
- 239000006258 conductive agent Substances 0.000 claims description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims description 18
- 159000000002 lithium salts Chemical class 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 17
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 9
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 9
- FVXHSJCDRRWIRE-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] FVXHSJCDRRWIRE-UHFFFAOYSA-H 0.000 claims description 6
- QWMBOURGUJLFKX-UHFFFAOYSA-N S(Cl)Cl.[P].[Li] Chemical compound S(Cl)Cl.[P].[Li] QWMBOURGUJLFKX-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- OCQSXFPWUMTHNA-UHFFFAOYSA-N [O-2].[Al+3].[Zr+4].[La+3].[Li+] Chemical compound [O-2].[Al+3].[Zr+4].[La+3].[Li+] OCQSXFPWUMTHNA-UHFFFAOYSA-N 0.000 claims description 6
- DGQGEJIVIMHONW-UHFFFAOYSA-N [O-2].[Ta+5].[Zr+4].[La+3].[Li+] Chemical compound [O-2].[Ta+5].[Zr+4].[La+3].[Li+] DGQGEJIVIMHONW-UHFFFAOYSA-N 0.000 claims description 6
- HALDOABDCFSGQQ-UHFFFAOYSA-N [P]=S.[Ge].[Li] Chemical compound [P]=S.[Ge].[Li] HALDOABDCFSGQQ-UHFFFAOYSA-N 0.000 claims description 6
- ZOJZLMMAVKKSFE-UHFFFAOYSA-N [P]=S.[Li] Chemical compound [P]=S.[Li] ZOJZLMMAVKKSFE-UHFFFAOYSA-N 0.000 claims description 6
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 6
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 claims description 6
- -1 lithium silicon phosphorus chlorosulfide Chemical compound 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
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- 238000000227 grinding Methods 0.000 claims description 4
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000007606 doctor blade method Methods 0.000 claims description 3
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- 239000002904 solvent Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
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- 230000000052 comparative effect Effects 0.000 description 9
- 239000011267 electrode slurry Substances 0.000 description 9
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 5
- 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 5
- 238000001000 micrograph Methods 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical group [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a positive pole piece and application thereof, wherein the positive pole piece comprises a positive pole piece main body and a solid electrolyte layer; the positive electrode plate main body comprises a positive electrode current collector and a positive electrode active layer arranged on at least one surface of the positive electrode current collector, and the solid electrolyte layer is at least arranged on the surface of the positive electrode active layer, which is far away from the positive electrode current collector; wherein the positive electrode active layer comprises a positive electrode active material, the positive electrode active material comprises a core material and a coating layer which at least covers part of the surface of the core material and comprises a first solid electrolyte material; the positive electrode plate is coated with the kernel material by the solid electrolyte to form a positive electrode active material, and the positive electrode active material and the solid electrolyte material are arranged on the surface of a positive electrode current collector to obtain the positive electrode plate with remarkably improved ion conductivity. The positive pole piece is beneficial to comprehensively improving interface impedance, improving the circulation capacity retention rate of the battery and reducing the internal resistance of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a positive pole piece and application thereof.
Background
Along with the popularization of new energy automobiles, the new energy automobile industry rises rapidly, and the development of the lithium ion battery market is driven along with the new energy automobile industry, so that the requirements of consumers on the safety performance of the electric automobile are also continuously improved. The lithium ion battery commonly used at present is a liquid phase battery, and the combustible organic electrolyte contained in the liquid phase battery has serious potential safety hazard.
The solid phase material is used as the electrolyte of the lithium ion battery, so that the potential safety hazard of combustion of the battery can be reduced, and the diaphragm is not required, so that the overall energy density (more than 300 Wh/kg) of the battery is improved. Therefore, the development of solid-state batteries with high energy density is a trend of lithium ion batteries in the future.
In solid-state batteries, the solid-state electrolyte serves the dual functions of ion conduction and separator. However, compared with the traditional liquid battery, the novel problems are brought about, mainly, the interface impedance between the solid electrolyte and the positive and negative electrode plates is large, the overall internal resistance of the battery is large, and the long-term electrical performance of the battery is poor, so that improvement of solid-solid interface contact is needed.
Disclosure of Invention
The invention provides a positive electrode plate, which solves the problem of larger interface impedance between a solid electrolyte and the positive electrode plate in a solid-state battery.
The invention provides a preparation method of a positive electrode plate, which is used for preparing the positive electrode plate and has the characteristic of high operability.
The invention also provides a battery which is used for solving the problems of large overall internal resistance and poor long-term electrical performance of the battery.
In one aspect, the invention provides a positive electrode sheet comprising a positive electrode sheet body and a solid electrolyte layer; the positive electrode plate main body comprises a positive electrode current collector and a positive electrode active layer arranged on at least one surface of the positive electrode current collector, and the solid electrolyte layer is at least arranged on the surface of the positive electrode active layer, which is far away from the positive electrode current collector;
wherein the positive electrode active layer comprises a positive electrode active material, and the positive electrode active material comprises a core material and a coating layer which at least covers part of the surface of the core material and comprises a first solid electrolyte material.
Further, the ionic conductivity of the first solid electrolyte material is not less than 10 -4 S/cm; and/or the number of the groups of groups,
the solid electrolyte layer includes a second solid electrolyte material having an ion conductivity of not less than 10 -4 S/cm。
Further, the first solid electrolyte material includes at least one of lithium lanthanum zirconium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum titanium oxide, titanium aluminum lithium phosphate, polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, germanium aluminum lithium phosphate, lithium phosphorus chlorosulfide, lithium silicon phosphorus chlorosulfide, lithium phosphorus sulfide, and lithium germanium phosphorus sulfide; and/or the number of the groups of groups,
the second solid electrolyte material includes at least one of lithium lanthanum zirconium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum titanium oxide, titanium aluminum lithium phosphate, polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, aluminum lithium germanium phosphate, lithium phosphorus chlorosulfide, lithium silicon phosphorus chlorosulfide, lithium phosphorus sulfide, and lithium germanium phosphorus sulfide.
Further, the first solid state electrolyte material and the second solid state electrolyte material are the same.
Further, the thickness of the solid electrolyte layer is 10-50 μm.
Further, the thickness of the coating layer is 10-100nm.
Further, in the positive electrode active layer, the mass ratio of the positive electrode active material, the conductive agent, the binder, the fast ion conductor and the lithium salt is (75-90): (1-8): (2-6): (0-10): (0-5).
On the other hand, the invention provides a preparation method of the positive plate, which comprises the following steps:
(1) Mixing the core material with a solution system comprising a first solid electrolyte material, drying the mixed system, and grinding and sieving to obtain a positive electrode active material with the particle size of 3-30 mu m;
(2) Setting positive slurry comprising the positive active material, a conductive agent, a binder, a fast ion conductor and lithium salt on the surface of the positive current collector in a doctor blade coating mode to obtain an intermediate positive plate; wherein the mass ratio of the positive electrode active material, the conductive agent, the binder, the fast ion conductor and the lithium salt is (75-90): (1-8): (2-6): (0-10): (0-5); the thickness of the coating is 10-100nm;
(3) Setting a slurry layer comprising a second solid electrolyte material on the surface of the middle positive electrode plate far away from the positive electrode current collector, and sequentially carrying out blast drying treatment and vacuum drying treatment to obtain the positive electrode plate, wherein the blast drying temperature is 60-100 ℃ and the drying time is 10-30min; vacuum drying temperature is 80-120 ℃ and drying time is 8-16h; the thickness of the slurry layer is 10-50 mu m.
In still another aspect, the invention further provides a battery, which comprises the positive electrode plate or the positive electrode plate obtained by the preparation method.
Further, the battery is a solid-state battery, and the solid-state electrolyte of the solid-state battery includes one or more of an oxide solid-state electrolyte, a polymer solid-state electrolyte, an oxide polymer composite electrolyte, and a sulfide electrolyte.
The invention provides a positive electrode plate, which is characterized in that a positive electrode active material is formed by coating a core material with solid electrolyte, and then the positive electrode active material and the solid electrolyte material are arranged on the surface of a positive electrode current collector, so that the positive electrode plate with remarkably improved ion conductivity is obtained; the positive pole piece is beneficial to comprehensively improving interface impedance, improving the circulation capacity retention rate of the battery and reducing the internal resistance of the battery.
Drawings
Fig. 1 is an ac impedance spectrum of a solid-state battery according to an embodiment of the present invention;
fig. 2 is a cycle performance diagram of a solid-state battery in an embodiment of the present invention;
FIG. 3 is a scanning electron microscope image of the positive electrode active material in example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of the core material of comparative example 1 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In one aspect, the invention provides a positive electrode sheet comprising a positive electrode sheet body and a solid electrolyte layer; the positive electrode plate main body comprises a positive electrode current collector and a positive electrode active layer arranged on at least one surface of the positive electrode current collector, and the solid electrolyte layer is at least arranged on the surface of the positive electrode active layer, which is far away from the positive electrode current collector;
wherein the positive electrode active layer includes a positive electrode active material including a core material and a coating layer including a first solid electrolyte material that coats at least a part of a surface of the core material.
Specifically, the positive electrode plate comprises a positive electrode plate main body and a solid electrolyte layer, wherein the positive electrode plate main body comprises a positive electrode current collector and a positive electrode active layer arranged on at least one surface of the positive electrode current collector, and the solid electrolyte layer is arranged on the surface of the positive electrode active layer, which is far away from the positive electrode current collector; the invention does not limit the type of the positive electrode current collector, and can realize the effect that electrons are generated between the positive electrode and the negative electrode and are conducted to an external loop, and preferably, the positive electrode current collector can be made of aluminum foil; the solid electrolyte layer is arranged on the surface of the positive electrode active layer, which is far away from the positive electrode current collector, so that the ion conduction performance of the pole piece can be improved, and the interface impedance can be reduced.
The positive electrode active layer comprises a positive electrode active material, wherein the positive electrode active material comprises a core material and a coating layer which at least covers part of the surface of the core material and comprises a first solid electrolyte material; the invention is also not limited to the type of the core material, and the lithium-containing oxide with a layered or tunnel structure is usually selected, preferably, the core material is one or more of ternary positive electrode, lithium cobaltate, lithium iron phosphate and lithium titanate materials, and the particle size distribution range of the core material is 2-50 μm; by providing the surface with a core material comprising a coating layer of a first solid electrolyte material, the inter-particle point-to-point contact can be improved, improving the interface resistance.
According to the positive electrode plate, the inner core material containing the coating layer of the first solid electrolyte material is arranged on the surface of the positive electrode plate, so that the point-to-point contact among particles is improved, the positive electrode active layer and the solid electrolyte layer are arranged on the surface of the positive electrode current collector together, the ion conductivity of the electrode plate is improved, the interface impedance is effectively reduced, and the full contact and stability of a solid-solid interface are ensured.
In one embodiment, the solid electrolyte layer is disposed on a surface of the positive electrode active layer remote from the positive electrode current collector.
In another embodiment, the solid electrolyte layer includes a first solid electrolyte layer and a second solid electrolyte layer, wherein the first solid electrolyte layer is distributed inside the positive electrode active layer, and the second solid electrolyte layer is disposed on a surface of the positive electrode active layer away from the positive electrode current collector.
In one embodiment, the ionic conductivity of the first solid electrolyte material is not less than 10 -4 S/cm；
In another embodiment, the solid electrolyte layer includes a second solidA state electrolyte material, the second solid electrolyte material having an ionic conductivity of not less than 10 -4 S/cm。
It will be appreciated that the first solid electrolyte material is included in the coating layer coated on the surface of the core material portion, and the present invention is not limited to the kind of the first solid electrolyte material, and preferably, when the ionic conductivity of the first solid electrolyte material is not less than 10 -4 When S/cm is adopted, the ion transmission between the middle points of the core material particles is quicker, and the interface impedance of the positive pole piece can be better improved;
the surface of the positive electrode current collector far away from the positive electrode active layer is provided with a solid electrolyte layer, the solid electrolyte layer comprises a second solid electrolyte, the invention is not limited to the type of the second solid electrolyte material, and preferably, the ionic conductivity of the second solid electrolyte material is not lower than 10 -4 S/cm, the ion conduction performance of the positive electrode plate can be further improved.
In a specific embodiment, the first solid state electrolyte material includes at least one of Lithium Lanthanum Zirconium Oxide (LLZO), lithium Lanthanum Zirconium Tantalum Oxide (LLZTO), lithium Lanthanum Zirconium Aluminum Oxide (LLZAO), lithium Lanthanum Titanium Oxide (LLTO), titanium aluminum lithium phosphate (LATP), polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), aluminum lithium germanium phosphate (langp), lithium phosphorus chlorosulfide (lipcl), lithium silicon phosphorus chlorosulfide (lisipcl), lithium phosphorus sulfide (LiPS), and lithium germanium phosphorus sulfide (liggeps);
in another embodiment, the second solid state electrolyte material includes at least one of Lithium Lanthanum Zirconium Oxide (LLZO), lithium Lanthanum Zirconium Tantalum Oxide (LLZTO), lithium Lanthanum Zirconium Aluminum Oxide (LLZAO), lithium Lanthanum Titanium Oxide (LLTO), titanium aluminum lithium phosphate (LATP), polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), aluminum lithium germanium phosphate (LAGP), lithium phosphorus chlorosulfide (lipcl), lithium silicon phosphorus chlorosulfide (lisipcl), lithium phosphorus sulfide (LiPS), and lithium germanium phosphorus sulfide (liggeps).
By further limiting the types of the first solid electrolyte material and the second solid electrolyte material, the ionic conductivity of the pole piece can be further improved, the internal resistance of the battery can be reduced, and the electrochemical performance of the pole piece can be improved.
Further, the first solid state electrolyte material and the second solid state electrolyte material are the same.
Wherein, the same may refer to the same substance, or may refer to a compound whose phases contain the same element; it can be appreciated that when the first solid electrolyte material and the second solid electrolyte material are the same, the positive electrode active layer and the solid electrolyte layer can perform a better synergistic effect, further improving the ionic conductivity of the pole piece and reducing the interface impedance.
Preferably, the thickness of the solid electrolyte layer is 10-50 μm.
It can be understood that the thickness of the solid electrolyte layer affects the ion conductivity of the positive electrode sheet, so that the problem that the positive electrode current collector is directly contacted with the solid electrolyte can be effectively avoided, and the inventor finds that when the thickness of the solid electrolyte layer is 10-50 μm, the internal resistance of the battery can be further reduced, and the capacity fade of the battery can be reduced.
Further, the thickness of the coating layer is 10-100nm.
It can be understood that the coating layer provided on the surface of the core material portion can improve the ion conductivity of the pole piece, and when the thickness of the coating layer is 10-100nm, the mass fraction of the first solid electrolyte contained in the coating layer is 0.01% -0.5%; the battery capacity retention rate can be further improved.
Specifically, in the positive electrode active layer, the mass ratio of the positive electrode active material, the conductive agent, the binder, the fast ion conductor and the lithium salt is (75-90): (1-8): (2-6): (0-10): (0-5).
In order to improve the performance of the positive electrode active layer, the positive electrode active layer comprises a conductive agent, a binder, a fast ion conductor and a lithium salt in addition to the positive electrode active material, wherein the mass ratio of the positive electrode active material to the conductive agent to the binder to the fast ion conductor to the lithium salt is (75-90): (1-8): (2-6): (0-10): (0-5);
wherein the conductive agent is at least one selected from conductive carbon black, ketjen black, carbon fiber, carbon nanotube and graphene; the binder is selected from at least one of PVDF and PVDF-HFP, PAN, PEO, PMMA; the fast ion conductor is selected from the group consisting of LLZO,LLZTO, LLZAO, LLTO, LATP, LAGP, liPSCl, liSiPSCl, liPS, liGePS; the lithium salt is selected from LiFSI, liTFSI, liPF 6 ，LiBF 4 ，LiDFOB，LiPO 2 F 2 At least one of (a) and (b); by further limiting the composition and the mass ratio of the positive electrode active layer, the lithium ion diffusion speed of the positive electrode plate can be further improved, and the interface performance is improved.
On the other hand, the invention provides a preparation method of the positive plate, which comprises the following steps:
(1) Mixing the core material with a solution system comprising a first solid electrolyte material, drying the mixed system, and grinding and sieving to obtain a positive electrode active material with the particle size of 3-30 mu m;
(2) Setting positive slurry comprising positive active material, conductive agent, adhesive, fast ion conductor and lithium salt on the surface of positive current collector by means of scraping and coating to obtain middle positive pole piece; wherein the mass ratio of the positive electrode active material, the conductive agent, the binder, the fast ion conductor and the lithium salt is (75-90): (1-8): (2-6): (0-10): (0-5); the thickness of the coating is 10-100nm;
(3) Setting a slurry layer comprising a second solid electrolyte material on the surface of the middle positive electrode plate far away from the positive electrode current collector, and sequentially carrying out blast drying treatment and vacuum drying treatment to obtain the positive electrode plate, wherein the blast drying temperature is 60-100 ℃ and the drying time is 10-30min; vacuum drying temperature is 80-120 ℃ and drying time is 8-16h; the thickness of the slurry layer is 10-50 mu m.
In the step (1), the core material is one or more of ternary positive electrode, lithium cobaltate, lithium iron phosphate and lithium titanate material, and the particle size distribution range of the core material is 2-50 mu m; the solvent of the solution system can be organic solvent, preferably comprises one or more of N-methyl pyrrolidone, dimethylformamide, ethanol, acetone, ethyl acetate, ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, propylene carbonate, benzene, alkane and ether;
specifically, adding a first solid electrolyte material into a solution system prepared by a solvent, and uniformly mixing the solution system by stirring, wherein the stirring speed is 100-1000rpm, the stirring time is 6-18h, and the stirring temperature is 25-40 ℃ to obtain a coating solution system comprising the first solid electrolyte material; then adding the core material into a mixed system to be mixed and dried, wherein the stirring speed is 100-1000rpm, the stirring time is 6-18h, the drying temperature is 60-120 ℃ and the drying time is 6-18h, and then grinding and sieving treatment are carried out to obtain the anode active material with the particle size of 3-30 mu m; the first solid electrolyte is coated on the core material, so that the solid-solid connection performance among the core material particles is further improved;
in the step (2), adding the positive electrode active material, the conductive agent, the binder, the fast ion conductor and the lithium salt into a solvent to prepare positive electrode slurry, wherein the solvent can be selected from one or more of organic solvents, preferably N-methyl pyrrolidone, dimethylformamide, ethanol, acetone, ethyl acetate, ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, propylene carbonate, benzene, alkanes and ethers; the fast ion conductor can be at least one of LLZO, LLZTO, LLZAO, LLTO, LATP, LAGP, liPSCl, liSiPSCl, liPS, liGePS; setting the positive slurry on the surface of a positive current collector by a scraper in a scraping and coating mode to obtain a middle positive plate; the ion conduction performance of the positive pole piece is further improved;
preferably, the mass ratio of the positive electrode active material, the conductive agent, the binder, the fast ion conductor and the lithium salt is (75-90): (1-8): (2-6): (0-10): (0-5); the thickness of the coating is 10-100nm, and the coating gap of the scraper is 100-300 mu m;
in the step (3), adding the second solid electrolyte material into the solvent, and uniformly mixing and stirring, wherein the stirring speed is 1000-5000rpm, the stirring time is 30-60min, and the stirring temperature is 25-40 ℃ to obtain electrolyte slurry; then, setting electrolyte slurry on the surface of the positive electrode active layer, which is far away from the positive electrode current collector, forming a slurry layer, and sequentially carrying out blast drying treatment and vacuum drying treatment to obtain a positive electrode plate; preferably, the electrolyte slurry is coated on the surface of the middle positive pole piece in a doctor blade coating mode; wherein the coating gap of the scraper is 100-300 mu m; the blast drying temperature is 60-100 ℃, the drying time is 10-30min, the vacuum drying temperature is 80-120 ℃, and the drying time is 8-16h.
In step (3), when the electrolyte slurry is disposed on the surface of the positive electrode active layer remote from the positive electrode current collector, a part of the electrolyte slurry may penetrate into the inside of the positive electrode active layer, and after the drying treatment, a solid electrolyte layer including a first solid electrolyte layer distributed in the inside of the positive electrode active layer and a second solid electrolyte layer located on the surface of the positive electrode active layer remote from the positive electrode current collector is obtained.
The invention provides a preparation method of the positive electrode plate, which comprises the steps of coating a first solid electrolyte with a core material to obtain a positive electrode active material, arranging the positive electrode active material on the surface of a positive electrode current collector to form a positive electrode active layer, and arranging a solid electrolyte layer comprising a second solid electrolyte on the surface of the positive electrode current collector far away from the positive electrode active layer, so that the contact between points among particles of the core material is improved, the interface impedance is effectively reduced, and the ion conductivity of the plate is improved.
In still another aspect, the invention further provides a battery, which comprises the positive electrode plate or the positive electrode plate obtained by the preparation method.
The invention provides a battery, which comprises the positive electrode plate, wherein the surface of the positive electrode plate is provided with a core material containing a coating layer of a first solid electrolyte material, and then the positive electrode active layer and the solid electrolyte layer are jointly arranged on the surface of a positive electrode current collector, so that the contact between the particles and the points is improved, the ion conductivity of the electrode plate is improved, the interface impedance is effectively reduced, the capacity circulation rate of the battery is improved, and the internal resistance of the battery is reduced.
Further, the battery is a solid-state battery, and the solid-state electrolyte of the solid-state battery includes one or more of an oxide solid-state electrolyte, a polymer solid-state electrolyte, an oxide polymer composite electrolyte, and a sulfide electrolyte.
The positive pole piece provided by the invention can further improve the ion conductivity of the solid-state battery and reduce the interface impedance of solid-solid contact.
The following describes a positive electrode sheet provided by the invention in detail through a specific embodiment.
Example 1
Preparing a positive electrode plate:
(1) 0.1g of ion conductivity 5 x 10 is weighed -4 Adding LATP of S/cm into 100g of ethanol solvent, and stirring for 6h to obtain coating solution; 100g Ni was weighed 0.8 Co 0.1 Mn 0.1 Li is added into the coating solution, stirred for 6 hours, dried by air blast at 80 ℃ for 12 hours, and the dried solid is ground and sieved to obtain the anode active material; the thickness of the coating layer is 30nm;
(2) Positive electrode active material, conductive agent (sp), binder (PVDF), fast ion conductor (LATP), lithium salt (LiTFSI) in proportion of 80:5:5:5:5 dispersing in N-methyl pyrrolidone solvent, stirring for 2 hours to obtain positive electrode slurry, uniformly coating the positive electrode slurry on aluminum foil by using a 200 mu m scraper, and drying at 100 ℃ for 10 minutes to obtain an intermediate positive electrode plate;
(3) 1g of LATP is weighed and added into 9g of dimethylformamide solvent, and the mixture is stirred for 60min to obtain electrolyte slurry; uniformly coating electrolyte slurry on the middle positive electrode plate by using a 200 mu m scraper, then carrying out air blast drying at 80 ℃ for 15min, and finally carrying out vacuum drying at 100 ℃ for 12h on the positive electrode plate to obtain a positive electrode plate; the solid electrolyte layer had a thickness of 10. Mu.m.
Example 2
This example differs from example 1 in that 0.5g LATP was added in step (1) and the thickness of the coating layer was 100nm.
Example 3
This example differs from example 1 in that the solid electrolyte layer thickness in step (3) is 50 μm.
Example 4
This example differs from example 1 in that 1g of the ionic conductivity of 10 was added in step (3) -4 S/cm of a mixture of PEO and LiTFSI.
Example 5
This example differs from example 1 in that 1g of LATP was added in step (1), and the thickness of the coating layer was 150nm.
Example 6
This example differs from example 1 in that the solid electrolyte layer thickness in step (3) is 80 μm.
Example 7
This example differs from example 1 in that 0.1g of ion conductivity 8.10 was added in step (1) -5 S/cm LiNbO 3 。
Comparative example 1
Preparing a positive electrode plate:
ni is added with 0.8 Co 0.1 Mn 0.1 Li, conductive agent (sp), binder (PVDF), fast ion conductor (LATP), lithium salt (LiTFSI) in proportion 80:5:5:5:5 dispersing in N-methyl pyrrolidone solvent, stirring for 2h to obtain positive electrode slurry, uniformly coating the positive electrode slurry on aluminum foil by using a 200 mu m scraper, and drying at 100 ℃ for 10min to obtain the positive electrode plate.
Comparative example 2
Preparing a positive electrode plate:
(1) Ni is added with 0.8 Co 0.1 Mn 0.1 Li, conductive agent (sp), binder (PVDF), fast ion conductor (LATP), lithium salt (LiTFSI) in proportion 80:5:5:5:5 dispersing in N-methyl pyrrolidone solvent, stirring for 2 hours to obtain positive electrode slurry, uniformly coating the positive electrode slurry on aluminum foil by using a 200 mu m scraper, and drying at 100 ℃ for 10 minutes to obtain an intermediate positive electrode plate;
(2) 1g of LATP is weighed and added into 9g of dimethylformamide solvent, and the mixture is stirred for 60min to obtain electrolyte slurry; uniformly coating electrolyte slurry on the middle positive electrode plate by using a 200 mu m scraper, then carrying out air blast drying at 80 ℃ for 15min, and finally carrying out vacuum drying at 100 ℃ for 12h on the positive electrode plate to obtain a positive electrode plate; the solid electrolyte layer had a thickness of 10. Mu.m.
Comparative example 3
Preparing a positive electrode plate:
(1) 0.1g of ion conductivity 5 x 10 is weighed -4 Adding LATP of S/cm into 100g of ethanol solvent, and stirring for 6h to obtain coating solution; weigh 100gNi 0.8 Co 0.1 Mn 0.1 Li is added into the coating solution, stirred for 6 hours, dried by air blast at 80 ℃ for 12 hours, and the dried solid is ground and sieved to obtain the anode active material; the thickness of the coating layer is 30nm;
(2) Positive electrode active material, conductive agent (sp), binder (PVDF), fast ion conductor (LATP), lithium salt (LiTFSI) in proportion of 80:5:5:5:5 dispersing in N-methyl pyrrolidone solvent, stirring for 2h to obtain positive electrode slurry, uniformly coating the positive electrode slurry on aluminum foil by using a 200 mu m scraper, and drying at 100 ℃ for 10min to obtain the positive electrode plate.
Test examples
1. Preparing a solid-state battery: and stacking the positive electrode plate, the PEO film, the lithium sheet, the gasket, the elastic sheet, the graphite and the silicon negative electrode in the battery shell in sequence, and assembling the solid-state battery.
The internal resistance values of the batteries and the cycle stability of the batteries were measured by the ac impedance/charge-discharge test for the solid-state batteries prepared in the above examples and comparative examples, and the results are shown in table 1 and fig. 1 and 2.
2. SEM examination was performed on example 1 and comparative example 1, resulting in fig. 3 and 4.
Fig. 3 is a scanning electron microscope image of the positive electrode active material in example 1 of the present invention, and fig. 4 is a scanning electron microscope image of the positive electrode active material in comparative example 1 of the present invention; as can be seen from fig. 3, the core material coated by the first solid electrolyte material forms the positive electrode active material, and coarse particles are arranged on the particle surface in the figure, which indicates that the LATP coating layer is successfully coated on the particle surface of the core material; comparing fig. 4, wherein the surface of the core material particles is smooth, it is proved that the core material is not coated with the coating material, and the combination of the internal resistance value of the battery and the cycle stability test of the battery shows that the coating layer formed on the surface of the core material is beneficial to improving the conductivity of the positive electrode plate and improving the interface property of solid-solid contact.
TABLE 1
As can be seen from table 1, referring to fig. 1 and 2, examples 1 to 4 show that the capacity retention rate after 100 cycles of the solid-state battery is 80% or more when the thickness of the coating layer is 30 to 100nm and the thickness of the solid-state electrolyte is 10 to 50 μm, and that the capacity retention rate after 100 cycles of the prepared battery is as high as 99.9% when the thickness of the coating layer is 30nm and the thickness of the solid-state electrolyte is 10 μm, and the internal resistance of the battery is minimum and is only 51Ω; from examples 5 to 7, the battery prepared from the positive electrode sheet provided by the application still has a capacity maintenance rate of about 80% after 100 cycles, has good long-term electrical performance, maintains the internal resistance at about 120 Ω, and remarkably reduces interface impedance; as can be seen from comparative example 1, when the core material is not coated and the positive electrode sheet is not coated with the electrolyte slurry, the capacity maintenance rate of the prepared solid-state battery after 100 cycles is only 58.9%, and as can be seen from comparative examples 2 and 3, when the prepared solid-state battery lacks the coating layer or lacks the coating layer, the capacity maintenance rate after 100 cycles is only about 70%, and the internal resistance of the battery is very high, and the interfacial resistance problem is not improved.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The positive electrode plate is characterized by comprising a positive electrode plate main body and a solid electrolyte layer; the positive electrode plate main body comprises a positive electrode current collector and a positive electrode active layer arranged on at least one surface of the positive electrode current collector, and the solid electrolyte layer is at least arranged on the surface of the positive electrode active layer, which is far away from the positive electrode current collector;
wherein the positive electrode active layer comprises a positive electrode active material, and the positive electrode active material comprises a core material and a coating layer which at least covers part of the surface of the core material and comprises a first solid electrolyte material.
2. The positive electrode sheet according to claim 1, characterized in thatThe ionic conductivity of the first solid electrolyte material is not less than 10 -4 S/cm; and/or the number of the groups of groups,
the solid electrolyte layer includes a second solid electrolyte material having an ion conductivity of not less than 10 -4 S/cm。
3. The positive electrode sheet of claim 2, wherein the first solid electrolyte material comprises at least one of lithium lanthanum zirconium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum titanium oxide, lithium aluminum titanium phosphate, polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, lithium aluminum germanium phosphate, lithium phosphorus chlorosulfide, lithium silicon phosphorus chlorosulfide, lithium phosphorus sulfide, and lithium germanium phosphorus sulfide; and/or the number of the groups of groups,
the second solid electrolyte material includes at least one of lithium lanthanum zirconium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium aluminum oxide, lithium lanthanum titanium oxide, titanium aluminum lithium phosphate, polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, aluminum lithium germanium phosphate, lithium phosphorus chlorosulfide, lithium silicon phosphorus chlorosulfide, lithium phosphorus sulfide, and lithium germanium phosphorus sulfide.
4. The positive electrode sheet of claim 3, wherein the first solid electrolyte material and the second solid electrolyte material are the same.
5. The positive electrode sheet according to any one of claims 1 to 4, wherein the thickness of the solid electrolyte layer is 10 to 50 μm.
6. The positive electrode sheet according to any one of claims 1 to 5, wherein the thickness of the coating layer is 10 to 100nm.
7. The positive electrode sheet according to any one of claims 1 to 6, wherein in the positive electrode active layer, the mass ratio of positive electrode active material, conductive agent, binder, fast ion conductor and lithium salt is (75 to 90): (1-8): (2-6): (0-10): (0-5).
8. A method for preparing the positive electrode sheet according to any one of claims 1 to 7, comprising the steps of:
(1) Mixing the core material with a solution system comprising a first solid electrolyte material, drying the mixed system, and grinding and sieving to obtain a positive electrode active material with the particle size of 3-30 mu m;
(2) Setting positive slurry comprising the positive active material, a conductive agent, a binder, a fast ion conductor and lithium salt on the surface of the positive current collector in a doctor blade coating mode to obtain an intermediate positive plate; wherein the mass ratio of the positive electrode active material, the conductive agent, the binder, the fast ion conductor and the lithium salt is (75-90): (1-8): (2-6): (0-10): (0-5); the thickness of the coating is 10-100nm;
(3) Setting a slurry layer comprising a second solid electrolyte material on the surface of the middle positive electrode plate far away from the positive electrode current collector, and sequentially carrying out blast drying treatment and vacuum drying treatment to obtain the positive electrode plate, wherein the blast drying temperature is 60-100 ℃ and the drying time is 10-30min; vacuum drying temperature is 80-120 ℃ and drying time is 8-16h; the thickness of the slurry layer is 10-50 mu m.
9. A battery comprising the positive electrode sheet according to any one of claims 1 to 7 or the positive electrode sheet obtained by the production method according to claim 8.
10. The battery of claim 9, wherein the battery is a solid state battery, and the solid state electrolyte of the solid state battery comprises one or more of an oxide solid state electrolyte, a polymer solid state electrolyte, an oxide polymer composite electrolyte, and a sulfide electrolyte.
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