CN117096482B - Battery cell structure and battery - Google Patents
Battery cell structure and battery Download PDFInfo
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- CN117096482B CN117096482B CN202311360576.4A CN202311360576A CN117096482B CN 117096482 B CN117096482 B CN 117096482B CN 202311360576 A CN202311360576 A CN 202311360576A CN 117096482 B CN117096482 B CN 117096482B
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- 239000000463 material Substances 0.000 claims abstract description 92
- 239000011149 active material Substances 0.000 claims abstract description 86
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 60
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 239000013132 MOF-5 Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 12
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 5
- 239000013118 MOF-74-type framework Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000011888 foil Substances 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- 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 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000013255 MILs Substances 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 10
- 239000010410 layer Substances 0.000 description 130
- 239000007789 gas Substances 0.000 description 51
- 210000004027 cell Anatomy 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005247 gettering Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- -1 Na + Chemical class 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
- H01M10/526—Removing gases inside the secondary cell, e.g. by absorption by gas recombination on the electrode surface or by structuring the electrode surface to improve gas recombination
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The battery cell structure comprises positive electrode plates and negative electrode plates which are alternately laminated, and composite electrode plates positioned on the outermost layer, wherein the polarities of the composite electrode plates and the positive electrode plates are opposite and the same as the polarities of the negative electrode plates, and the polarities of the composite electrode plates are opposite to the polarities of one of the positive electrode plates and the negative electrode plates, which is close to the composite electrode plates; the composite electrode plate comprises a first current collector, a first active material layer and a MOFs material layer, and the MOFs material layer is far away from the positive electrode plate; the positive plate comprises a second current collector and a second active material layer; the negative electrode sheet comprises a third current collector and a third active material layer, wherein the thickness and the sectional area of each material layer simultaneously satisfy: q×d×m is not less than 95% ×n×d 2 ×b×m 2 ，d=0.9D 3 ~1.1D 3 ，D 1 =D 3 =a×D 2 ，m=m 1 =m 3 ,m=1.0m 2 ~1.1m 2 . Through the design, the MOFs material layer is effectively suitable for adsorbing gas generated by the cell structures with different capacities.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a battery cell structure and a battery.
Background
Batteries are widely used in various industries as energy storage media. The safety of the traditional all-liquid lithium ion battery is questioned all the time because the traditional all-liquid lithium ion battery adopts liquid electrolyte. With the continuous breakthrough and progress of the battery industry technology, the battery is gradually changed from an all-liquid battery to a semi-solid battery, and finally, the battery is moved to an all-solid battery. The all-solid-state battery has the advantages of high safety, high energy density and the like, and is a hot topic of research in the current scientific research field and the industry. However, various studies have shown that in practical use of solid state batteries, gas is generated for a variety of reasons, for example, in polymer-based solid state lithium cobalt oxide batteries, lattice oxygen on the surface of the detached lithium cobalt oxide cathode material can bond with PEO, reducing the reaction energy of the dehydrogenation reaction, leading to HTFSI formation and hydrogen generation. In all-solid-state batteries of high-nickel positive electrode-phosphorothioate solid-state electrolyte systems, however, the carbonate on the surface of the positive electrode material still undergoes decomposition after charging, thereby generating gas. The problem of gassing is particularly pronounced during cycling, storage, and once generated, the flooding of the electrode with these gases will deteriorate the solid electrolyte to active material interface and even block lithium ion transport, resulting in battery degradation. Therefore, how to solve the gas production is a problem that must be solved.
Disclosure of Invention
The invention aims to solve the problem that the gas produced by the solid-state battery stays in the electrode after circulation and storage and influences the service life, thereby providing a cell structure with the surface capable of adsorbing the gas, effectively removing the gas produced in the battery and remarkably prolonging the service life of the solid-state battery.
The invention provides a battery cell structure, which comprises positive plates and negative plates which are alternately laminated, and composite electrode plates positioned on the outermost layer, wherein the polarities of the composite electrode plates and the positive plates are opposite, the polarities of the composite electrode plates and the negative plates are the same, the polarities of the composite electrode plates are opposite to the polarity of one, close to the composite electrode plates, of the positive plates and the negative plates, and the battery cell structure is provided with N layers of positive plates, N-1 layers of negative plates and 2 layers of composite electrode plates, and N is more than or equal to 2;
the composite electrode plate comprises a first current collector, a first active material layer positioned on one side of the first current collector and a MOFs material layer positioned on the other side of the first current collector, and the MOFs material layer is far away from the positive electrode plate; the positive plate comprises a second current collector and second active material layers positioned on two sides of the second current collector; the negative electrode sheet includes a third current collector and third active material layers located on both sides of the third current collector.
Further, the MOFs material layer comprises MOFs materials, and the MOFs materials are one or more of MOF-5, MOF-74, ZIF-8 and MIL 101.
The invention also provides a battery, which comprises any one of the battery core structures.
The invention has the beneficial effects that:
1) Since one surface of the negative electrode active material on each of the outermost negative electrodes is not utilized in the normal battery structural design, the simplified process is generally present, and the energy density is reduced to some extent while the material is wasted. The invention introduces a novel MOFs material to replace the outermost layer, so that waste is avoided, and the high-pore structure of the MOFs material is utilized to largely adsorb oxidative and/or reductive gases generated in the circulating and storing processes of the solid-state battery. Thus solving the negative influence caused by gas production on the premise of not reducing the energy density of the battery. The MOFs material has high heat resistance and stability, and after the service life of the battery is finished, the material can be recycled to replace the oxidative and/or reductive gas adsorbed in the material for reuse, so that the MOFs material is energy-saving and environment-friendly.
2) Through the thickness ratio between each layer of the cell structure, the MOFs material layer can effectively adapt to the adsorption of gases generated by the cell structures with different capacities.
Drawings
FIG. 1 is a schematic diagram of one embodiment of a cell structure of the present invention;
reference numerals illustrate:
1. a cell structure; 2. a composite electrode sheet; 3. a positive plate; 4. a negative electrode sheet; 21. a first current collector; 22. a first active material layer; 23. a layer of MOFs material; 31. a second current collector; 32. a second active material layer; 41. a third current collector; 42. and a third active material layer.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present application, the present invention will be further described with reference to the accompanying drawings and specific embodiments, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, shall fall within the scope of the present application.
In this specification, the relevant descriptions of parts and proportions are referred to by weight unless otherwise indicated.
In the present specification, the second active material layerUnit volume gas production measurement b=solid state battery total gas production u 1 Total volume v of the second active material layer 2 Wherein b is in mu mol/mm 3 ，u 1 In mu mol, v 2 In mm 3 . When the MOFs material layer is included in the solid-state battery, the total gas yield of the solid-state battery is not directly measured because the MOFs material has gettering property. Therefore, in order to obtain the gas production measurement value b of the unit volume of the second active material layer, the invention adopts a conventional solid-state battery (the cell structure of the conventional solid-state battery comprises N layers of positive plates and N+1 layers of negative plates which are alternately laminated, MOFs material layers are not contained, N is more than or equal to 2; the outermost layer of the conventional solid-state battery is the negative plate, and 2 layers of second active material layers are arranged on each positive plate), and the gas production test is carried out by the specific test method as follows: the prepared conventional solid-state battery was cycled at 60 deg.C and 5V using 1C rate, and the generated gas was V at a standard atmospheric pressure and 25 deg.C when the capacity retention rate was decayed from the initial 100% SOH to 80% SOH 1 mL (gas molar volume at 25 ℃ C., one standard atmosphere is 24.5L/mol), the solid-state battery total gas yield u 1 = 1000×v 1 24.5. Mu. Mol. Total volume v of the second active material layer 2 =2n×second active material layer monolayer volume, second active material layer monolayer volume=thickness D of second active material layer 2 X cross-sectional area m 2 ，D 2 In mm, m 2 In mm 2 The cross-sectional area refers to an area perpendicular to the thickness direction. Thus, the second active material layer gas production measurement value b=solid-state battery total gas production amount u per unit volume 1 Total volume v of the second active material layer 2 =（1000×v 1 / 24.5）/ (2N×D 2 ×m 2 ). Testing the main component of the gas generated by the conventional solid-state battery, e.g. CO 2 In the case of battery design, CO is preferable 2 MOFs materials with high adsorption capacity, such as MOF-5, ZIF-8; for example, the gas has a main component H 2 When designing the battery, H is preferable 2 MOFs materials with a strong adsorption capacity. For example, the conventional solid-state battery in comparative example 1 produces the main bodyThe gas being CO 2 The batteries prepared in examples 2 to 13 were made of the same positive and negative electrode materials as in comparative example 1, and the main gas components generated were comparable to those in comparative example 1, so that the batteries of examples 2 to 13 were designed using CO 2 MOF-5 material or ZIF-8 material with strong adsorption capacity.
Example 1
Referring to fig. 1, a cell structure 1 includes positive electrode sheets 3 and negative electrode sheets 4 alternately stacked, and composite electrode sheets 2 positioned at the outermost layer, the polarities of the composite electrode sheets 2 and the positive electrode sheets 3 are opposite, the polarities of the composite electrode sheets 2 and the negative electrode sheets 4 are the same, and the polarity of the composite electrode sheets 2 is opposite to the polarity of one of the positive electrode sheets 3 and the negative electrode sheets 4, which is close to the composite electrode sheets 2. That is, among the positive electrode sheet 3 and the negative electrode sheet 4, the composite electrode sheet 2 is closer to the positive electrode sheet 3. The battery cell structure is provided with N layers of positive electrode plates, N-1 layers of negative electrode plates and 2 layers of composite electrode plates, and N is more than or equal to 2. Fig. 1 shows that when n=2, the electrode sheet in the cell structure 1 includes 2 layers of composite electrode sheets 2, 2 layers of positive electrode sheets 3 and 1 layer of negative electrode sheets 4. When n=3, the cell structure has 3 layers of positive plates, 2 layers of negative plates and 2 layers of composite electrode plates (not shown in fig. 1), and so on.
The composite electrode sheet 2 includes a first current collector 21, a first active material layer 22 located at one side of the first current collector 21, and a MOFs material layer 23 located at the other side of the first current collector 21. The composite electrode sheet 2 is the outermost electrode sheet of the cell structure 1, and the first active material layer 22 faces the positive electrode sheet, and the MOFs material layer 23 is far away from the positive electrode sheet. The positive electrode sheet 3 includes a second current collector 31 and second active material layers 32 located at both sides of the second current collector 31.
The current collector is a foil and may be a metal such as aluminum or copper. The current collector of the composite electrode sheet 2 is preferably copper foil; the current collector of the positive electrode sheet 3 is preferably aluminum foil.
The first active material layer 22 includes therein a negative active material, which may be one or more of graphite, a silicon material, hard carbon, soft carbon, lithium metal, sodium metal, and other alloying materials. MOFs material is included in MOFs material layer 23. MOFs (Metal Organic Frameworks, metal-organic bones)The scaffold compound) is an organic-inorganic hybrid material, and is formed by connecting an inorganic metal center and a crosslinked organic ligand through self-assembly, so that a crystalline porous material with a periodic network structure is formed. MOFs material has ultra-high porosity and high specific surface area (100-10000 m 2 And/g), the pore size (3-100A) can be regulated, thus being very suitable for being used as a gas adsorption material, and utilizing the characteristics thereof to adsorb oxidative and/or reductive gases generated in the solid-state battery, such as carbon dioxide, hydrogen, methane, ethane and the like, thereby solving the negative influence caused by gas generation of the solid-state battery. Meanwhile, the MOFs material has high thermal stability (up to 500 ℃) and excellent chemical stability, can adapt to the internal environment of the battery, and cannot be damaged. Specifically, the MOFs material can be one or more of MOF-5, MOF-74, ZIF-8, MIL101 and MOF-808. In general, in the case where the composite electrode sheet 2 is not curled, there may be a certain difference in thickness of the first active material layer 22 and the MOFs material layer 23. Preferably, the thickness of the first active material layer 22 is the same as that of the MOFs material layer 23, so that the stress on both sides of the current collector can be balanced, and the curling phenomenon of the composite electrode sheet 2 can be avoided.
The second active material layer 32 includes a positive electrode active material of lithium nickel cobalt manganese oxide, lithium cobalt oxide, lithium manganese iron phosphate, lithium-rich manganese, na x MO 2 Layered oxide (M is mainly one or more of transition metal elements), prussian blue analogues, or polyanion sodium salt. The Prussian blue analogues have the general formulaWherein A is an alkali metal, e.g. Na + 、K + Etc.; m is M 1 And M 2 Is a different coordination transition metal ion (wherein M 1 Coordinated with N, M 2 Coordinated to C), such as Mn, fe, co, ni, cu, zn, cr, etc.; />Is->And (5) a vacancy. In general, in the case where the positive electrode sheet 3 is not curled, there may be a certain difference in thickness of the second active material layer 32 located at both sides of the second current collector 31. Preferably, the second active material layers 32 located at both sides of the current collector have the same thickness.
The negative electrode sheet 4 includes a third current collector 41 and third active material layers 42 located at both sides of the third current collector 41. The third active material layer 42 includes a negative active material, which may be one or more of graphite, a silicon material, hard carbon, soft carbon, lithium metal, sodium metal, and other alloying materials. Preferably, the third active material layer 42 is identical to the first active material layer 22. In general, in the case where the negative electrode sheet 4 is not curled, there may be a certain difference in thickness of the third active material layer 42 located at both sides of the third current collector 41. Preferably, the third active material layers 42 located at both sides of the current collector have the same thickness. The composite electrode sheet 2 and the negative electrode sheet 4 are usually made of the same current collector, preferably copper foil.
Example 2
Preparing a positive plate, a composite electrode plate and a negative plate. The positive electrode sheet includes a second current collector (aluminum foil) and second active material layers located at both sides of the second current collector. The second active material layer comprises 85 parts of nickel cobalt lithium manganate (NCM 811), 2 parts of conductive carbon black (Super-P), 10 parts of Lithium Aluminum Titanium Phosphate (LATP) and 3 parts of polyvinylidene fluoride. The composite electrode sheet includes a first current collector (copper foil), a first active material layer located on one side of the first current collector, and a MOFs material layer located on the other side of the first current collector. The first active material layer comprises 80 parts of silicon material, 2 parts of conductive carbon black (Super-P), 15 parts of Lithium Aluminum Titanium Phosphate (LATP) and 3 parts of polyvinylidene fluoride. The negative electrode sheet includes a third current collector (copper foil) and third active material layers located on both sides of the third current collector. The proportion and thickness of the third active material layer are equal to those of the first active material layer. The third current collector is identical to the first current collector, and the same copper foil is used, and the thickness, surface roughness and the like of the copper foil are the same. The mixture ratio of the MOFs material layer is 95 parts of MOF-5 material and 5 parts of polyvinylidene fluoride. First active material layer and third active materialThe density of the material layer is 1.5g/cm 3 . The thickness of the second active material layer is 70 mu m, the thickness of the second current collector is 12 mu m, the thicknesses of the first active material layer and the third active material layer are 90 mu m, the thicknesses of the first current collector and the third current collector are 5 mu m, and the thickness of the MOF-5 material layer is 90 mu m. The cross-sectional areas of the first active material layer, the third active material layer and the MOF-5 material layer are all 100mm multiplied by 300mm; the second active material layer has a cross-sectional area of 98mm by 297mm. The cross-sectional area refers to an area perpendicular to the thickness direction. And (3) enabling the MOF-5 material layer of the composite electrode plate to be far away from the positive electrode plate. And (5) welding and packaging the battery core structure after lamination to obtain the solid-state battery. The solid-state battery has 38 layers of positive plates, 37 layers of negative plates and 2 layers of composite electrode plates. The solid-state battery comprises MOFs material layers, and the total gas yield of the solid-state battery is not directly measured due to the gas absorption performance of the MOFs material, so that the gas production test is carried out by adopting the solid-state battery prepared in comparative example 1.
Example 3
The solid-state battery was prepared in the same manner as in example 2, except that the MOFs material on the composite electrode sheet of this example was ZIF-8. The solid-state battery has 38 layers of positive plates, 37 layers of negative plates and 2 layers of composite electrode plates. The ZIF-8 material layer thickness is 90 mu m. The solid-state battery comprises MOFs material layers, and the total gas yield of the solid-state battery is not directly measured due to the gas absorption performance of the MOFs material, so that the gas production test is carried out by adopting the solid-state battery prepared in comparative example 1.
Comparative example 1
The solid-state battery preparation method was the same as in example 2 except that the composite electrode sheet of example was replaced with the negative electrode sheet entirely. The solid-state battery produced had 38 layers of positive electrode sheets and 39 layers of negative electrode sheets.
The solid-state battery prepared in comparative example 1 was cycled at 60℃and 5V using a 1C rate, and the volume of gas generated when the capacity retention rate was decayed from the initial 100% SOH to 80% SOH was 78.4mL at 25℃under a standard atmospheric pressure, and the gas generated was mainly CO 2 、CO、O 2 、H 2 The volume ratio of each gas is CO 2 ：CO：O 2 ：H 2 =72: 15:8:5, dividing 78.4mL by 24.5. 24.5L/mol to obtain 3.2mmol of mixed gas, wherein the gas component is mainly CO 2 Therefore, CO was used in examples 2 to 3 2 MOF-5 material and ZIF-8 material with strong adsorption capacity.
The positive electrode active material (second active material layer) and the negative electrode active material (first active material layer and/or third active material layer) of examples 2 and 3 are identical to those of comparative example 1, and the negative electrode active material of the outermost layer of comparative example 1 is not responsible for gas generation, so the gas generation amounts of examples 2 and 3 are identical to those of comparative example 1, i.e., the solid-state battery total gas generation amount u 1 3.2mmol. The second active material layer of examples 2 and 3 was measured for gas production per unit volume, b, from the total gas production u of the solid-state battery 1 Divided by the total volume v of the second active material layer for the battery 2 And it follows that b=u 1 /v 2 = u 1 /（2N×D 2 ×m 2 ）=（3.2×10 3 ）/（2×38×0.07mm×98mm×297mm）= 0.0207μmol/mm 3 。
The solid-state batteries prepared in example 2, example 3 and comparative example 1 were subjected to cycle and storage tests, and the cycle life and the rate of change in external shape and volume were measured, and the results are shown in table 1.
The number of cycles experienced as the capacity retention decays from an initial 100% soh to 80% soh using a 1C rate cycle of the battery is the cycle life. From the results of table 1, it can be seen that the addition of MOFs material can increase the cycle life of the solid state battery and absorb the generated gas inside the material without affecting the whole battery. After the design of the invention, the service life of the solid-state battery is obviously optimized.
As can be seen from the results of table 2, in the case of using the MOFs material layer having the same thickness as the first active material layer, both examples 2 and 3 can increase the battery energy density and specific power at the same time on the premise of absorbing a certain gas to improve the cycle life, compared to comparative example 1. Furthermore, the MOFs material layer has extremely high porosity and is a metal-organic framework compound, so that the MOFs material layer has certain flexibility. The flexible MOFs coating is coated on the outermost two sides of the electrode in the battery, which is equivalent to protecting the two sides of the battery, and can protect the battery from damage when the battery is impacted, extruded and impacted by external force.
Examples 4 to 13
Through the design of the cell structure, the MOFs material layer can effectively adapt to the adsorption of gases generated by the cell structures with different capacities. As the capacity of the battery cell increases, the amounts of the corresponding positive electrode active material and negative electrode active material also need to be increased, the generation of gas also increases, and the gettering capability per unit volume of the MOFs material layer is fixed. The theoretical adsorption capacity of the MOFs material layer can be obtained from known literature or manufacturers, and Table 3 lists theoretical adsorption values per unit mass of carbon dioxide for a portion of the MOFs material at a standard atmospheric pressure, and a value selected from a range of values for the theoretical adsorption capacity is used as a design, and is based on the density of the MOFs material (e.g., MOF-5 material density of about 0.3g/cm 3 ZIF-8 material has a density of about 0.15g/cm 3 MOF-74 material density was about 0.6 g/cm 3 MIL101 material density was about 0.58g/cm 3 ) The theoretical value q of the inspiration of the unit volume of the MOFs material layer can be obtained.
In examples 2 to 13, the theoretical amount of carbon dioxide absorbed by the ZIF-8 material at a standard atmospheric pressure was 5mmol/g, and the density was about 0.15g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The theoretical inspiration of carbon dioxide at a standard atmospheric pressure for the MOF-5 material was chosen to be 2mmol/g and the density was approximately 0.3g/cm 3 . The theoretical value of inspiration per unit volume of the ZIF-8 material layer=5 mmol/g×0.15g/cm 3 =0.75 μmol/mm 3 The method comprises the steps of carrying out a first treatment on the surface of the Theoretical air suction per unit volume of MOF-5 material layer=2 mmol/g×0.3g/cm 3 =0.6 μmol/mm 3 。
The battery cell structure is provided with N layers of positive electrode plates, N-1 layers of negative electrode plates and 2 layers of composite electrode plates, wherein N is more than or equal to 2; thickness D of the second active material layer 2 Cross-sectional area m 2 The method comprises the steps of carrying out a first treatment on the surface of the Thickness D of first active material layer 1 Cross-sectional area m 1 The method comprises the steps of carrying out a first treatment on the surface of the Thickness D of the third active Material layer 3 Cross-sectional area m 3 The method comprises the steps of carrying out a first treatment on the surface of the The thickness d and the sectional area m of the MOFs material layer. q×d×m is not less than 95% ×n×d 2 ×b×m 2 ，d=0.9D 3 ~1.1D 3 B is a measured value of gas production per unit volume of the second active material layer, and q is a theoretical value of gas absorption per unit volume of the MOFs material layer. The cross-sectional area refers to an area perpendicular to the thickness direction. The principle of charging and discharging the lithium ion battery is that lithium ions are separated from the positive electrode and are inserted into the negative electrode during charging; the opposite is true when discharging. The lithium ion released from the positive electrode can be completely inserted into the negative electrode, otherwise, electrons can be obtained on the surface of the negative electrode when the lithium ion cannot be completely inserted in the charging process, so that a lithium metal simple substance is formed. The lithium metal simple substance is continuously accumulated, lithium dendrites are formed, and the gas production of the battery is increased, so that the safety problem is caused, and the service life of the battery is influenced. In order to avoid the formation of lithium dendrites by the generation of excess lithium ions, it is ensured that lithium ions from the positive electrode are all absorbed by the negative electrode, on the one hand, m=m is designed 1 =m 3 , m=1.0m 2 ~1.1m 2 ，D 1 =D 3 =a×D 2 A is the thickness coefficient of the second active material layer; on the other hand, after the positive electrode active material (second active material layer) and the negative electrode active material (first active material layer and/or third active material layer) are selected, a is required 1 A is less than or equal to 2, wherein a is less than or equal to 2 1 For the thickness coefficient, a, of the second active material layer, in which theoretically lithium ions from the positive electrode are absorbed exactly by the negative electrode 1 The value of (2) may be determined by the capacity of the positive and negative electrode active materials, the theoretical ultimate compaction density, which is an intrinsic property of the materials, and may be obtained from known literature or manufacturers; the larger a is, the more excessive design of the anode active material wastes the material and causes the reduction of the energy density of the battery, and the battery comprehensive performance in the range of a < 2 is better in comprehensive consideration. For example: capacity C of positive electrode active material 1 Is 210mAh/g, theoretical ultimate compaction density T 1 3.6g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Capacity C of anode active material 2 600mAh/g, theoretical ultimate compaction density T 2 1.6g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then a 1 =(C 1 ×T 1 )/(C 2 ×T 2 ) The minimum value of a is 0.79=0.79. By the above design, on the basis of satisfying the air suction effect, a cell structure with low integrated energy density and large specific power can be preferable, for example: compared with example 3, examples 4 to 5 have a lower energy density and a higher specific power, and examples 6 to 7 have a higher energy density and a lower specific power. In addition, on the basis of meeting the air suction effect, the number of layers of the positive plate is increased to improve the energy density, the thickness of the corresponding MOFs material layer and the thickness of the negative plate active material layer are increased to reduce the energy density, and therefore the energy density of the battery is reduced finally, but the specific power is increased; further, in examples 11 to 13, the decrease in the number of layers of the positive electrode active material brings about a decrease in energy density, and the decrease in the thickness of the corresponding MOFs material layer and the thickness of the negative electrode active material layer brings about an increase in energy density, which ultimately results in an increase in energy density and a decrease in specific power. It can be understood that the invention can also design the cell structure according to the relation between the thickness and the cross-sectional area of each material layer on the basis of meeting the air suction effect according to the energy density and the specific power of the expected battery, for example: examples 8 to 13.
The materials used for the positive electrode sheet, the negative electrode sheet and the composite electrode sheet are referred to in the above examples 2 and 3, and the cell structure design is performed by changing the relevant parameters, and the specific changed parameters are shown in table 4 and table 5.
Claims (5)
1. The battery cell structure is characterized by comprising positive electrode plates and negative electrode plates which are alternately laminated, and compound electrode plates positioned on the outermost layer, wherein the polarities of the compound electrode plates and the positive electrode plates are opposite, the polarities of the compound electrode plates and the negative electrode plates are the same, the polarities of the compound electrode plates are opposite to the polarity of one, close to the compound electrode plates, of the positive electrode plates and the negative electrode plates, and the battery cell structure is provided with N layers of positive electrode plates, N-1 layers of negative electrode plates and 2 layers of compound electrode plates, and N is more than or equal to 2;
the composite electrode plate comprises a first current collector, a first active material layer positioned on one side of the first current collector and a MOFs material layer positioned on the other side of the first current collector, wherein the MOFs material layer is far away from the positive electrode plate, and the thickness D of the first active material layer 1 Cross-sectional area m 1 The thickness d and the sectional area m of the MOFs material layer;
the positive plate comprises a second current collector and second active material layers positioned on two sides of the second current collector, wherein the thickness D of the second active material layers 2 Cross-sectional area m 2 ；
The negative electrode sheet comprises a third current collector and third active material layers positioned on two sides of the third current collector, wherein the thickness D of the third active material layers 3 Cross-sectional area m 3 ；
The thickness and the sectional area of each material layer simultaneously satisfy the following formula:
q×d×m ≥95%×N×D 2 ×b×m 2 ，
d=0.9D 3 ~1.1D 3 ，D 1 =D 3 =a×D 2 ，
m=m 1 =m 3 , m=1.0m 2 ~1.1m 2 ，
wherein q is the theoretical value of inspiration per unit volume of MOFs material layer, b is the measured value of gas production per unit volume of the second active material layer, a is the thickness coefficient of the second active material layer, and a 1 ≤a＜2， a 1 The thickness coefficient of the second active material layer is the thickness coefficient of the second active material layer, which is theoretically that lithium ions of the positive electrode plate are exactly absorbed by the negative electrode plate; the cross-sectional area refers to an area perpendicular to the thickness direction.
2. The cell structure of claim 1, wherein the first active material layer and the MOFs material layer are the same thickness.
3. The cell structure of claim 1, wherein the MOFs material is one or more of MOF-5, ZIF-8, MOF-74, or MILs 101.
4. The cell structure of claim 2, wherein the first current collector is copper foil, the second current collector is aluminum foil, and the third current collector is the same as the first current collector; the first active material layer comprises 80 parts of silicon material, 2 parts of conductive carbon black, 15 parts of lithium aluminum titanium phosphate and 3 parts of polyvinylidene fluoride; the second active material layer comprises 85 parts of nickel cobalt lithium manganate, 2 parts of conductive carbon black, 10 parts of aluminum titanium lithium phosphate and 3 parts of polyvinylidene fluoride; the proportion and thickness of the third active material layer are the same as those of the first active material layer; the mixture ratio of the MOFs material layer is 95 parts of MOF-5 material or ZIF-8 material and 5 parts of polyvinylidene fluoride; the thickness of the second active material layer is 70 mu m, the thickness of the second current collector is 12 mu m, the thicknesses of the first active material layer and the third active material layer are 90 mu m, the thicknesses of the first current collector and the third current collector are 5 mu m, and the thickness of the MOF-5 material layer is 90 mu m; the cross-sectional areas of the first active material layer, the third active material layer and the MOF-5 material layer are all 100mm multiplied by 300mm; the second active material layer has a cross-sectional area of 98mm by 297mm; the battery cell structure is provided with 38 layers of positive electrode plates, 37 layers of negative electrode plates and 2 layers of composite electrode plates.
5. A battery comprising the cell structure of any one of claims 1-4.
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