CN115084523A - Electrode slurry and preparation method and application thereof - Google Patents
Electrode slurry and preparation method and application thereof Download PDFInfo
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- CN115084523A CN115084523A CN202210746713.7A CN202210746713A CN115084523A CN 115084523 A CN115084523 A CN 115084523A CN 202210746713 A CN202210746713 A CN 202210746713A CN 115084523 A CN115084523 A CN 115084523A
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- 239000011267 electrode slurry Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000011149 active material Substances 0.000 claims abstract description 67
- 238000000859 sublimation Methods 0.000 claims abstract description 65
- 230000008022 sublimation Effects 0.000 claims abstract description 65
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 63
- 239000003795 chemical substances by application Substances 0.000 claims description 73
- 239000006258 conductive agent Substances 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 8
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 29
- 238000000354 decomposition reaction Methods 0.000 abstract description 14
- 238000010438 heat treatment Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- 238000011056 performance test Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 229910021389 graphene Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011883 electrode binding agent Substances 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 5
- 239000002003 electrode paste Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241001089723 Metaphycus omega Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000003013 cathode binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- -1 chloroparaffins Chemical compound 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- GBCAVSYHPPARHX-UHFFFAOYSA-M n'-cyclohexyl-n-[2-(4-methylmorpholin-4-ium-4-yl)ethyl]methanediimine;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1CCCCC1N=C=NCC[N+]1(C)CCOCC1 GBCAVSYHPPARHX-UHFFFAOYSA-M 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000032258 transport Effects 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses electrode slurry and a preparation method and application thereof. According to the invention, the sublimation agent is added into the electrode slurry, and the vertical aggregated bubbles generated by heating and sublimation of the sublimation agent are utilized to construct the directional pore channel in the active material layer, so that the porosity of the active material layer can reach 45%, the active material layer has no decomposition residue, the internal resistance of the electrode plate is reduced, and the pores of the active material layer are relatively uniform, so that the lithium ion battery comprising the electrode plate has higher rate capability and longer cycle life.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to electrode slurry as well as a preparation method and application thereof.
Background
In recent years, with rapid development of new energy vehicles, electronic communication devices, and the like, consumers increasingly demand lithium ion batteries having characteristics of high capacity, long life, high stability, and high energy density. Therefore, the development of a lithium ion battery having high energy density and fast charging capability is important for portable electronic products and electric vehicles. The electrode is a key factor determining the performance of the battery, and currently, research on the electrode in the lithium ion battery mainly focuses on modification of an electrode material, research and development of a novel electrode material, design of an electrode structure and the like. Among them, increasing the loading of active materials of electrodes is the most direct method for increasing the energy density of batteries, and thus the thickness of electrode sheets is inevitably increased. The increase in the thickness of the electrode sheet lengthens the charge transfer path, resulting in the reaction kinetics in the thick electrode becoming slower. Especially at high rates, slow charge transport limits the charge capacity and power density of the battery.
In addition to electrode materials, electrode structure design is also one of the means to improve battery performance. The porous electrode is an electrode with a certain porosity, and the porous electrode is used for carrying out electrochemical reaction, so that the surface area participating in the electrode reaction can be increased, the electrochemical polarization is reduced, and the current density during charging and discharging is reduced. In the porous electrode, the performance of the electrode is closely related to an electronic conductive network formed by solid-phase conductive particles and a liquid-phase ion transport network formed by electrolyte in pores. The electron conductive network and the ion transmission network are influenced by the structural parameters of the porous electrode, namely, the microstructure parameters of the electrode, such as porosity, pore size and distribution, tortuosity, electrode component distribution and the like, are key factors for determining the performance of the electrode and the battery. The porous electrode structure directly influences the performance of the battery, and the good pore structure and the proper distribution of the electrode components can improve the performance of the electrode. Therefore, optimizing the structural design of the electrode becomes an important technical approach to improve the high energy density of the lithium ion battery.
Methods for preparing porous electrodes have also been proposed in the prior art, for example, by adding pore-forming polymers (polymers or copolymers such as polyalkylene carbonates, polyalkylene oxides, polyalkylsiloxanes, polyalkylacrylates, polyalkylmethacrylates, etc.) or pore-forming agents (ammonium bicarbonate, ammonium carbonate, chloroparaffins, urea, ammonium chloride, etc.) to the electrode slurry, which pore-forming polymers or pore-forming agents act to form pores within the active material layer. The pore-forming polymer or pore-forming agent generates gas through pyrolysis and forms pores in the active material layer, but the pyrolysis also generates other non-gas products, and the decomposition products remain in the active material layer, so that the internal resistance of the active material layer is increased, and the performance of the lithium ion battery is finally affected. In addition, the thermal decomposition of the pore-forming polymer or pore-forming agent is an explosive decomposition process, and the generation of bubbles is concentrated, so that the pore size of the pores formed in the active material layer is greatly different, thereby affecting the diffusion rate of lithium ions in the active material layer.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide electrode slurry and a preparation method and application thereof. According to the invention, the sublimation agent is added into the electrode slurry, and the vertical aggregated bubbles generated by heating and sublimation of the sublimation agent are utilized to construct the directional pore channel in the active material layer, so that the porosity of the active material layer can reach 45%, the active material layer has no decomposition residue, the internal resistance of the electrode plate is reduced, and the pores of the active material layer are relatively uniform, so that the lithium ion battery comprising the electrode plate has higher rate capability and longer cycle life.
In one aspect of the invention, an electrode paste is provided. According to an embodiment of the present invention, the electrode paste includes an active material substance, a binder, a conductive agent, a sublimation agent, and a solvent.
According to the electrode slurry disclosed by the embodiment of the invention, the sublimation agent is added into the electrode slurry, and the oriented pore channel is constructed in the active material layer by utilizing vertically aggregated bubbles generated by heating and sublimation of the sublimation agent, so that the porous electrode plate is formed. From this, increased the area of contact of active material layer with electrolyte for lithium ion is at the diffusion of active material layer, has increased the liquid absorption volume of active material layer to electrolyte moreover, thereby guarantee the sufficiency of circulation in-process electrolyte, make the lithium ion battery who contains above-mentioned electrode slice have higher rate performance and cycle life. Meanwhile, after the sublimation agent in the electrode slurry is heated and sublimated, the gaseous sublimation agent escapes from the dried active material layer and hardly remains in the active material layer, so that the problem that the internal resistance of the active material layer is increased due to the fact that a decomposition product is remained after the pore-forming agent adopted in the prior art is heated and decomposed is solved. In addition, the sublimating agent is slowly and gradually sublimated after being heated, and the generation of bubbles is smooth, so that the pore passages formed in the active material layer are relatively uniform, and the problem that the bubbles generated by the heated decomposition of the pore-forming agent in the prior art are relatively concentrated is solved.
In addition, the electrode paste according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the present invention, the sublimation agent is contained in an amount of 1% to 20% based on the total mass of the active material substance, the binder, the conductive agent, and the sublimation agent.
In some embodiments of the present invention, the sublimation agent is contained in an amount of 5% to 10% based on the total mass of the active material substance, the binder, the conductive agent, and the sublimation agent.
In some embodiments of the present invention, the mass ratio of the active material species, the binder, the conductive agent, and the sublimation agent is (80-95): (0.5-2): (1-20).
In some embodiments of the invention, the sublimation agent is selected from at least one of iodine, naphthalene, anthracene, and trioxymethylene.
In yet another aspect of the present invention, an electrode sheet is provided. According to the embodiment of the invention, the electrode plate is prepared from the electrode slurry described in the above embodiment. Therefore, the porosity of the active material layer in the electrode plate can reach 45%, no decomposition residues exist in the electrode plate, the internal resistance of the electrode plate is reduced, and the pores of the electrode plate are relatively uniform, so that the lithium ion battery comprising the electrode plate has higher rate performance and longer cycle life.
In a third aspect of the present invention, the present invention provides a method of preparing the above electrode sheet. According to an embodiment of the invention, the method comprises:
(1) mixing an active material substance, a binder, a conductive agent, a sublimation agent, and a solvent to obtain an electrode slurry;
(2) and coating the electrode slurry on the surface of a current collector, and drying to obtain the electrode plate.
According to the method for preparing the electrode plate, the preparation method is simple and easy to implement, and the porosity and the uniformity of pores of the electrode plate are controllable.
In addition, the method for preparing the electrode sheet according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the temperature of the drying is 60-80 ℃.
In a fourth aspect of the present invention, a lithium ion battery is presented. According to an embodiment of the invention, the lithium ion battery has the electrode sheet described in the above embodiment. Therefore, the rate capability and the cycle life of the lithium ion battery are further improved.
In a fifth aspect of the present invention, an electric vehicle is provided. According to an embodiment of the present invention, the electric vehicle has the lithium ion battery as described above. Therefore, the electric vehicle loaded with the lithium battery with excellent rate performance and cycle life has excellent cruising ability, thereby meeting the use requirements of consumers.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
Reference will now be made in detail to the embodiments of the present invention, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The following described embodiments are exemplary and are intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, an electrode paste is provided. According to an embodiment of the present invention, an electrode paste includes an active material substance, a binder, a conductive agent, a sublimation agent, and a solvent. Therefore, the sublimation agent is added into the electrode slurry, and the vertical aggregated bubbles generated by sublimation of the sublimation agent under heating form a directional pore channel in the active material layer, so that the porosity of the active material layer can reach 45%, the active material layer has no decomposition residue, the internal resistance of the electrode plate is reduced, and the pores of the active material layer are relatively uniform, so that the lithium ion battery comprising the electrode plate has higher rate capability and longer cycle life.
Specifically, by adding the sublimation agent into the electrode slurry, when the electrode slurry is coated on the surface of the current collector and dried, the sublimation agent is heated to sublimate, the solid sublimation agent is changed into the gaseous sublimation agent, the gaseous sublimation agent escapes from the dried active material layer, and the directional pore channel is remained in the active material layer in the escaping process, so that the porous electrode plate is formed. From this, increased the area of contact of electrode slice with electrolyte, moreover because more open pore structure to and whole shorter diffusion distance, accelerated the diffusion of lithium ion, increased the liquid absorption volume of pole piece electrolyte simultaneously, thereby guarantee the abundant of circulation in-process electric liquid, make the lithium ion battery who contains above-mentioned electrode slice have higher multiplying power performance and cycle life.
Particularly, after the sublimation agent in the electrode slurry is heated and sublimated, the gaseous sublimation agent escapes from the dried active material layer and hardly remains in the active material layer, so that the problem that the internal resistance of the active material layer is increased due to the fact that a decomposition product remains after the pore-forming agent adopted in the prior art is heated and decomposed is solved. However, in the prior art, the porosity of the active material layer can also be increased by adopting a scheme that the pore-forming polymer or the pore-forming agent is thermally decomposed to form pores in the active material layer, but the pore-forming polymer or the pore-forming agent is thermally decomposed to generate other non-gaseous products besides gas, and the decomposition products can remain in the active material layer, so that the internal resistance of the active material layer is increased, and the performance of the lithium ion battery is finally affected. Alternatively, the decomposition product may form an inorganic substance such as lithium sulfide or lithium nitride together with lithium ions, and the inorganic substance may be dispersed in the active material layer, which may also increase the internal resistance of the active material layer. The solution of the invention using sublimating agent solves the above mentioned problems.
Specifically, the sublimation agent is slowly and gradually sublimated after being heated, and the generation of bubbles is relatively smooth, so that the pore passages formed in the active material layer are relatively uniform; in the prior art, the pore-forming agent is decomposed only when the pore-forming agent reaches the decomposition temperature, the thermal decomposition is an explosive decomposition process, and bubbles are generated more intensively, so that the pore size of pores formed in the active material layer has a larger difference, and the diffusion speed of lithium ions in the active material layer and the rate capability of the electrode plate are influenced.
According to an embodiment of the present invention, the content of the sublimation agent is 1% to 20%, for example, 1/2/4/6/8/10/12/14/16/18/20%, preferably 5% to 10%, based on the total mass of the active material substance, the binder, the conductive agent, and the sublimation agent, whereby the content of the sublimation agent is limited to the above range, the active material has a suitable porosity, and the lithium ion battery has a higher rate capability and a longer cycle life. Specifically, if the content of the sublimation agent is too low, the porosity of the formed active material layer is too low, the diffusion of lithium ions in the active material layer cannot be effectively accelerated, the contact area between the active material layer and the electrolyte cannot be effectively increased, and the liquid absorption amount of the active material layer to the electrolyte cannot be effectively increased; if the content of the sublimation agent is too high, the porosity of the formed active material layer is too high, the energy density of the electrode sheet is reduced, and the electrode sheet is easy to collapse.
In the embodiment of the present invention, a specific kind of the sublimation agent is not particularly limited as long as the sublimation agent can be sublimated during the drying process of the electrode sheet, and as a preferable mode, the sublimation agent is at least one selected from iodine, naphthalene, anthracene and trioxymethylene.
In the embodiment of the present invention, the electrode slurry may be a positive electrode slurry or a negative electrode slurry, and when the electrode slurry is a positive electrode slurry, the positive electrode slurry includes a positive electrode active material substance, a positive electrode binder, a positive electrode conductive agent, a sublimation agent, and a positive electrode solvent.
Specifically, the specific kind of the positive electrode active material substance is not particularly limited, and as some specific examples, the positive electrode active material substance may be at least one of lithium iron phosphate, a ternary positive electrode material NCM, a ternary positive electrode material NCA, and a binary positive electrode material.
Specifically, the specific kind of the above-mentioned cathode binder is not particularly limited, and as some specific examples, the above-mentioned cathode binder may be at least one of polyvinylidene fluoride, polyacrylic acid, N-methylpyrrolidone, dimethylformamide, and dimethylsulfoxide.
Specifically, the specific kind of the above positive electrode conductive agent is not particularly limited, and as some specific examples, the above positive electrode conductive agent may be at least one of super conductive carbon, carbon nanotubes, graphene, and conductive graphite.
Specifically, the specific kind of the above-mentioned cathode solvent is not particularly limited, and as some specific examples, the above-mentioned cathode solvent may be at least one of ethanol, acetone, N-methylpyrrolidone, dimethylformamide, and dimethylsulfoxide.
According to another embodiment of the present invention, the mass ratio of the positive electrode active material substance, the positive electrode binder, the positive electrode conductive agent, and the sublimation agent is (80-95): (0.5-2): (1-20), so that the content of each component is limited within the above range, and not only is the energy density of the positive electrode sheet fully ensured, but also the positive electrode sheet is ensured to have appropriate porosity, such that the lithium ion battery comprising the electrode sheet has higher rate capability and cycle life.
In an embodiment of the present invention, when the above-mentioned electrode slurry is a negative electrode slurry, the negative electrode slurry includes a negative electrode active material substance, a negative electrode binder, a negative electrode conductive agent, a sublimation agent, and a negative electrode solvent.
Specifically, the specific kind of the above negative electrode active material substance is not particularly limited, and as some specific examples, the above negative electrode active material substance may be at least one of artificial graphite, composite graphite, natural graphite, silicon carbon, silicon monoxide, mesocarbon microbeads, soft carbon, and hard carbon.
Specifically, the specific kind of the above negative electrode binder is not particularly limited, and as some specific examples, the above negative electrode binder may be at least one of polyacrylic acid PAA, polybutadiene-b-polystyrene, and sodium carboxymethyl cellulose and CMC.
Specifically, the specific kind of the negative electrode conductive agent is not particularly limited, and as some specific examples, the negative electrode conductive agent may be at least one of SP, carbon nanotube, and graphene.
Specifically, the specific kind of the above-mentioned anode solvent is not particularly limited, and as some specific examples, the above-mentioned anode solvent may be at least one of deionized water, acetonitrile, N-methylpyrrolidone, N-dimethylacetamide, and acetone.
According to still another embodiment of the present invention, the mass ratio of the negative electrode active material substance, the negative electrode binder, the negative electrode conductive agent, and the sublimation agent is (80-95): (0.5-2): (1-20), and thus, the content of each component is limited to the above range, which not only sufficiently ensures the energy density of the negative electrode sheet, but also ensures that the negative electrode sheet has a suitable porosity, so that the lithium ion battery including the electrode sheet has a higher rate capability and a longer cycle life.
In yet another aspect of the present invention, an electrode sheet is provided. According to the embodiment of the invention, the electrode plate is prepared from the electrode slurry prepared in the embodiment. Therefore, the porosity of the active material layer in the electrode plate can reach 45%, no decomposition residues exist in the electrode plate, the internal resistance of the electrode plate is reduced, and the pores of the electrode plate are relatively uniform, so that the lithium ion battery comprising the electrode plate has higher rate performance and longer cycle life.
In a third aspect of the present invention, the present invention provides a method of preparing the above electrode sheet. According to an embodiment of the invention, the method comprises:
s100: mixing active material substance, binder, conductive agent, subliming agent and solvent
In this step, the active material substance, the binder, the conductive agent, and the sublimating agent are simultaneously dissolved in the solvent and uniformly mixed, so as to obtain the electrode slurry.
S200: coating the electrode slurry on the surface of a current collector, and drying
In the step, the electrode slurry is coated on the surface of a current collector and dried, sublimation agent is heated to sublimate, solid sublimation agent is changed into gaseous sublimation agent, the gaseous sublimation agent escapes from the dried active material layer, and the directional pore channel is remained in the active material layer in the escaping process, so that the porous electrode plate is formed.
According to the method for preparing the electrode plate, the preparation method is simple and easy to implement, and the porosity and the uniformity of pores of the electrode plate are controllable. Specifically, the sublimation agent is heated to sublimate, the sublimation speed of the sublimation agent depends on the heated temperature of the sublimation agent, the higher the temperature is, the faster the sublimation speed of the sublimation agent is, the more gas is generated, the larger the pore diameter of the sublimation agent formed in the active material layer is, and therefore, the porosity and the uniformity of pores of the electrode plate can be controlled by controlling the drying temperature of the electrode plate. In addition, the sublimation agent needs to be sublimated at a relatively low temperature, while the pore-forming agent in the prior art generally needs to be heated and decomposed at a relatively high temperature, and the electrode plate can be aged due to the high temperature.
According to another embodiment of the present invention, the drying temperature may be 60-80 ℃, for example 60/65/70/75/80 ℃, so that in this temperature range, the sublimation agent is ensured to slowly and gradually sublimate, so as to form relatively uniform pores in the active material layer, and the adverse effect on the electrode sheet caused by too high drying temperature is avoided.
In a fourth aspect of the invention, a lithium ion battery is provided. According to an embodiment of the invention, the lithium ion battery has the electrode plate of the above embodiment. Therefore, the rate capability and the cycle life of the lithium ion battery are further improved.
In a fifth aspect of the present invention, an electric vehicle is provided. According to an embodiment of the present invention, the electric vehicle has the lithium ion battery as described above. Therefore, the electric vehicle loaded with the lithium battery with excellent rate performance and cycle life has excellent cruising ability, thereby meeting the use requirements of consumers.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
(1) Preparing a positive plate:
5 percent of trioxymethylene and 92 percent of LiFePO 4 And simultaneously adding 1.5% of positive binder PVDF and 1.5% of positive conductive agent graphene into positive solvent NMP, and uniformly mixing and stirring to obtain positive slurry with solid content of 50%. And coating the positive electrode slurry on a positive electrode current collector, and drying at 80 ℃ to obtain a positive electrode plate. The positive plate was subjected to lithium battery resistance test, and as a result, the plate resistance of the positive plate was 0.42 m.OMEGA./100. mu.m.
(2) Preparing a negative plate:
adding 96% of graphite, 2% of negative electrode binder polyacrylic acid and 2% of negative electrode conductive agent graphene into negative electrode solvent water at the same time, and uniformly mixing and stirring to obtain negative electrode slurry with the solid content of 50%. And coating the negative electrode slurry on a negative electrode current collector, and drying at 80 ℃ to obtain a negative electrode sheet.
(3) Preparing a lithium ion battery:
winding the positive plate, the negative plate and the diaphragm into a winding core, baking, entering a shell, injecting liquid and forming to obtain the lithium ion battery, wherein the electrolyte is 1M LiPF 6 EC/EMC (3:7) electrolyte of (1).
(4) And (3) testing:
the rate performance test of the lithium ion battery prepared in the above manner shows that the discharge capacity of the lithium ion battery prepared in this example at 2C is 1590 mAh.
The prepared lithium ion battery is subjected to cycle performance test, and the lithium ion battery is subjected to charge-discharge cycle at room temperature at 1C/1C, has the initial capacity of 2000mAh/g, is cycled for 3000 circles, has the specific capacity of 1700mAh/g, and shows good cycle performance.
Example 2
(1) Preparing a positive plate:
5 percent of trioxymethylene, 5 percent of iodine and 87 percent of LiFePO 4 And adding 1.5% of positive binder PVDF and 1.5% of positive conductive agent graphene into a positive solvent NMP at the same time, and uniformly mixing and stirring to obtain positive slurry with the solid content of 50%. And coating the positive electrode slurry on a positive electrode current collector, and drying at 70 ℃ to obtain a positive electrode plate. The positive plate was subjected to lithium battery resistance test, and as a result, the plate resistance of the positive plate was 0.41 m.OMEGA./100. mu.m.
(2) The negative electrode sheet was prepared as in example 1.
(3) The lithium ion battery was prepared as in example 1.
(4) And (3) testing:
the rate performance test of the lithium ion battery prepared above shows that the discharge capacity of the lithium ion battery prepared in this example at 2C is 1620 mAh.
The prepared lithium ion battery is subjected to cycle performance test, and the lithium ion battery is subjected to charge-discharge cycle at room temperature at 1C/1C, has the initial capacity of 2000mAh/g, is cycled for 3000 circles, keeps the specific capacity of 1750mAh/g, and shows good cycle performance.
Example 3
(1) Preparing a positive plate:
10% of trioxymethylene, 5% of naphthalene and 82% of LiFePO are mixed 4 And adding 1.5% of positive binder PVDF and 1.5% of positive conductive agent graphene into a positive solvent NMP at the same time, and uniformly mixing and stirring to obtain positive slurry with the solid content of 50%. And coating the positive electrode slurry on a positive electrode current collector, and drying at 60 ℃ to obtain a positive plate. The resistance test of the lithium battery is carried out on the positive plate, and the resistance of the positive plate is 0.4m omega/100 mu m.
(2) The negative electrode sheet was prepared as in example 1.
(3) The lithium ion battery was prepared as in example 1.
(4) And (3) testing:
the rate performance test of the lithium ion battery prepared in the above manner shows that the discharge capacity of the lithium ion battery prepared in this example at 2C is 1650 mAh.
The prepared lithium ion battery is subjected to cycle performance test, and the lithium ion battery is subjected to charge-discharge cycle at room temperature at 1C/1C, has the initial capacity of 2000mAh/g, is circulated for 3000 circles, has the specific capacity of 1800mAh/g, and shows good cycle performance.
Example 4
(1) Preparing a positive plate:
5 percent of trioxymethylene, 10 percent of anthracene and 82 percent of LiFePO 4 And adding 1.5% of positive binder PVDF and 1.5% of positive conductive agent graphene into a positive solvent NMP at the same time, and uniformly mixing and stirring to obtain positive slurry with the solid content of 50%. And coating the positive electrode slurry on a positive electrode current collector, and drying at 80 ℃ to obtain a positive electrode plate. The resistance test of the lithium battery is carried out on the positive plate, and the resistance of the positive plate is 0.4m omega/100 mu m.
(2) The negative electrode sheet was prepared as in example 1.
(3) The lithium ion battery was prepared as in example 1.
(4) And (3) testing:
the rate performance test of the lithium ion battery prepared in the above manner shows that the discharge capacity of the lithium ion battery prepared in this embodiment at 2C is 1650 mAh.
The prepared lithium ion battery is subjected to cycle performance test, and the lithium ion battery is subjected to charge-discharge cycle at room temperature at 1C/1C, has the initial capacity of 2000mAh/g, is circulated for 3000 circles, has the specific capacity of 1800mAh/g, and shows good cycle performance.
Example 5
(1) Preparing a positive plate:
97 percent of LiFePO 4 And adding 1.5% of positive binder PVDF and 1.5% of positive conductive agent graphene into a positive solvent NMP at the same time, and uniformly mixing and stirring to obtain positive slurry with the solid content of 50%. And coating the positive electrode slurry on a positive electrode current collector, and drying at 80 ℃ to obtain a positive electrode plate.
(2) Preparing a negative plate:
simultaneously adding 5% of trioxymethylene, 91% of graphite, 2% of negative electrode binder polyacrylic acid and 2% of negative electrode conductive agent graphene into a negative electrode solvent, and uniformly mixing and stirring to obtain negative electrode slurry with solid content of 50%. And coating the negative electrode slurry on a negative electrode current collector, and drying at 80 ℃ to obtain a negative electrode sheet. And performing lithium battery resistance test on the negative plate, wherein the resistance of the negative plate is 0.6m omega/100 mu m.
(3) Preparing a lithium ion battery:
winding the positive plate, the negative plate and the diaphragm into a winding core, baking, entering a shell, injecting liquid and forming to obtain the lithium ion battery, wherein the electrolyte is 1M LiPF 6 EC/EMC (3:7) electrolyte of (1).
(4) And (3) testing:
the rate performance test of the lithium ion battery prepared in the above manner shows that the discharge capacity of the lithium ion battery prepared in this example at 2C is 1590 mAh.
The prepared lithium ion battery is subjected to cycle performance test, and the lithium ion battery is subjected to charge-discharge cycle at room temperature at 1C/1C, has the initial capacity of 2000mAh/g, is cycled for 3000 circles, keeps the specific capacity of 1750mAh/g, and shows good cycle performance.
Comparative example 1
In this comparative example, no sublimation agent was added to the positive electrode slurry, and the rest was the same as in example 1.
The positive electrode sheet of this comparative example was subjected to lithium battery resistance test, and as a result, the sheet resistance of the positive electrode sheet was 0.6 m.OMEGA./100. mu.m.
The rate performance test of the lithium ion battery prepared by the comparative example shows that the discharge capacity of the lithium ion battery prepared by the comparative example is 1500mAh under 2C.
The lithium ion battery prepared by the comparative example is subjected to a cycle performance test, and the initial capacity is 2000mAh/g, the cycle is 2500 circles and the specific capacity is maintained to be 1600mAh/g through 1C/1C charge-discharge cycle at room temperature.
It can be seen that the rate performance and cycle performance of examples 1-5 are significantly improved compared to comparative example 1. The positive electrode sheets of examples 1 to 4 had smaller sheet resistance than comparative example 1.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. An electrode slurry is characterized by comprising an active material substance, a binder, a conductive agent, a sublimation agent, and a solvent.
2. The electrode slurry according to claim 1, wherein the content of the sublimation agent is 1% to 20% based on the total mass of the active material substance, the binder, the conductive agent, and the sublimation agent.
3. The electrode slurry according to claim 2, wherein the content of the sublimation agent is 5% to 10% based on the total mass of the active material substance, the binder, the conductive agent, and the sublimation agent.
4. The electrode slurry according to claim 2, wherein the mass ratio of the active material substance, the binder, the conductive agent, and the sublimation agent is (80-95): (0.5-2): (1-20).
5. The electrode slurry according to any one of claims 1 to 4, wherein the sublimation agent is selected from at least one of iodine, naphthalene, anthracene and trioxymethylene.
6. An electrode sheet, characterized by being prepared from the electrode slurry according to any one of claims 1 to 5.
7. A method of making the electrode sheet of claim 6, comprising:
(1) mixing an active material substance, a binder, a conductive agent, a sublimation agent, and a solvent to obtain an electrode slurry;
(2) and coating the electrode slurry on the surface of a current collector, and drying to obtain the electrode plate.
8. The method of claim 7, wherein the temperature of the drying is 60-80 ℃.
9. A lithium ion battery having the electrode sheet according to claim 6.
10. An electric vehicle comprising the lithium ion battery according to claim 9.
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