CN114005954B - Negative electrode sheet and electrochemical device - Google Patents
Negative electrode sheet and electrochemical device Download PDFInfo
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- CN114005954B CN114005954B CN202111260322.6A CN202111260322A CN114005954B CN 114005954 B CN114005954 B CN 114005954B CN 202111260322 A CN202111260322 A CN 202111260322A CN 114005954 B CN114005954 B CN 114005954B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002071 nanotube Substances 0.000 claims abstract description 12
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 7
- 239000013543 active substance Substances 0.000 claims abstract description 5
- 238000004804 winding Methods 0.000 claims description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 239000010439 graphite Substances 0.000 claims description 23
- 229910002804 graphite Inorganic materials 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 22
- 238000005452 bending Methods 0.000 claims description 15
- 239000007773 negative electrode material Substances 0.000 claims description 14
- 239000006183 anode active material Substances 0.000 claims description 11
- 239000010410 layer Substances 0.000 description 73
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 238000000576 coating method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 239000006258 conductive agent Substances 0.000 description 10
- 239000002270 dispersing agent Substances 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 239000011267 electrode slurry Substances 0.000 description 9
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- -1 for example Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
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- 238000002360 preparation method Methods 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001289 polyvinyl ether Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 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
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 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
- H01M4/13—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
- 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
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a negative electrode sheet and an electrochemical device, wherein the negative electrode sheet comprises a negative electrode current collector with a first section and a second section which are connected, a first negative electrode active layer positioned on the surface of the first section, and a second negative electrode active layer positioned on the surface of the second section, the first negative electrode active layer comprises a first negative electrode active substance, and the first negative electrode active substance comprises titanium dioxide nanotubes. The invention can improve the low-temperature performance of the cathode plate and the electrochemical device.
Description
Technical Field
The invention relates to a negative plate and an electrochemical device, and belongs to the field of electrochemical energy storage devices.
Background
With the advent of the electronic age, the portable power source has been widely used in various aspects, and the use conditions of various electronic devices have also gradually increased requirements on the performance of electrochemical devices such as lithium ion batteries, especially in low-temperature environments such as high-altitude areas and high-latitude areas. At present, electrochemical devices such as lithium ion batteries have poor low-temperature performance, poor specific discharge capacity at low temperature, and even normal charge and discharge are difficult, and the reasons for the poor low-temperature performance are mainly as follows: (1) The viscosity of the electrolyte is low at low temperature, and the ionic conductivity is obviously reduced; (2) The compatibility of the electrolyte with the negative electrode and the diaphragm at low temperature is poor, the normal transmission of lithium ions is affected, and the diffusion capacity of the lithium ions in the active material is reduced; and (3) the negative electrode is easy to precipitate lithium at low temperature. Therefore, how to improve the low-temperature performance of an electrochemical device is an important issue faced by those skilled in the art.
Disclosure of Invention
The invention provides a negative plate and an electrochemical device, which have good low-temperature performance and can effectively overcome the defects existing in the prior art.
In one aspect of the invention, a negative electrode sheet is provided, comprising a negative electrode current collector having a first section and a second section connected to each other, a first negative electrode active layer on a surface of the first section, and a second negative electrode active layer on a surface of the second section, wherein the first negative electrode active layer contains a first negative electrode active material, and the first negative electrode active material comprises titanium dioxide nanotubes.
According to an embodiment of the present invention, the first negative electrode active material further includes a graphite-based material; and/or the second anode active layer comprises a second anode active material comprising a graphite-based material.
According to an embodiment of the present invention, in the first negative electrode active material, the mass ratio of the titanium dioxide nanotube to the graphite-based material is (45 to 97): 5.
According to an embodiment of the present invention, in the first negative electrode active layer, the mass content of the titanium dioxide nanotube is 2% to 10%.
According to an embodiment of the present invention, it is satisfied that a/b is (0.45 to 0.65) 1, a is a length of the first segment in a direction from the first segment to the second segment, and b is a sum of a length of the first segment in a direction from the first segment to the second segment and a length of the second segment in a direction from the first segment to the second segment.
According to an embodiment of the invention, the first section comprises a first portion and a second portion connected, the second portion being located between the first portion and the second section; one surface of the first part is provided with the first negative electrode active layer, two surfaces of the second part are provided with the first negative electrode active layer, and two surfaces of the second section are provided with the second negative electrode active layer.
According to an embodiment of the invention, the negative electrode tab is provided with a negative electrode tab, which is arranged on the first section.
In another aspect of the present invention, there is provided an electrochemical device including the above-described negative electrode sheet.
According to one embodiment of the invention, the negative electrode sheet comprises at least two first straight parts and first bending parts connected between every two first straight parts, the negative electrode sheet is bent through the first bending parts to form a winding structure, and the first sections and the second sections are sequentially distributed along the winding direction of the winding structure from inside to outside.
According to one embodiment of the present invention, the first straight portion of the first section of the negative electrode tab located at the outermost side of the winding structure is provided with a negative electrode tab along the winding direction of the winding structure from inside to outside.
In the invention, the negative electrode active layer is arranged on the negative electrode plate in a segmented way, and the titanium dioxide (TiO 2) nano tube is introduced into the negative electrode active layer (namely the first negative electrode active layer) of the first section, so that the low-temperature performance of the negative electrode plate and an electrochemical device adopting the negative electrode plate can be improved, the phenomenon of low-temperature lithium precipitation is inhibited, the low-temperature discharge capacity of the negative electrode plate is improved, and the method is specifically characterized in that: the discharge capacity at-10 ℃ and 0.4C rate can reach more than 84 percent, and the discharge capacity at-20 ℃ and 0.2C rate can reach more than 70 percent. According to research and analysis of the inventor, the TiO 2 nanotube has smaller diameter, short ion (such as lithium ion) diffusion path, large specific surface area and good dynamics performance; meanwhile, the TiO 2 nano tube is used as a negative electrode active material of a lithium ion battery, has small volume strain (less than 4 percent), has higher potential than lithium, and can avoid the formation of lithium dendrite, thereby improving the phenomenon of low-temperature lithium precipitation; in addition, tiO 2 nano-tubes intercalate lithium with negative active substances such as Yu Danmo base materials with high potential (1.5V), lithium is intercalated into an electrochemical device firstly during charging, ohmic heat is generated due to current circulation in the lithium intercalation process, and the temperature of a battery cell of the electrochemical device is increased, so that the viscosity of electrolyte is improved, the compatibility of the electrolyte with a negative plate and a diaphragm is improved, the ion conductivity and the diffusion capacity of the electrolyte in the active materials are improved, and the problem of low-temperature lithium precipitation is further relieved. Therefore, the invention can obviously improve the low-temperature performance of electrochemical devices such as lithium ion batteries and the like, and has important significance for practical industrial application.
Drawings
Fig. 1 is a schematic view of a negative electrode sheet according to an embodiment of the present invention;
fig. 2 is a schematic diagram of a winding type cell according to an embodiment of the invention.
Reference numerals illustrate:
1: a negative electrode sheet;
2: a positive plate;
3: a diaphragm;
11: a first section;
12: a second section;
13: a negative electrode tab;
14: a first bending part;
21: a first second straight portion;
22: a second bending part;
23: a positive electrode tab;
101: a first anode active layer;
102: a second anode active layer;
111: a first section;
112: a second section;
1101: a first straight portion;
1104: a fourth first straight portion;
A: a first surface of the negative electrode current collector;
c: and a second surface of the negative electrode current collector.
Detailed Description
The present invention will be described in further detail below for the purpose of better understanding of the aspects of the present invention by those skilled in the art. The following detailed description is merely illustrative of the principles and features of the present invention, and examples are set forth for the purpose of illustration only and are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the examples of the invention without making any inventive effort, are intended to be within the scope of the invention. In the description of the present invention, the terms "first", "second", etc. are used for descriptive purposes only, for example to distinguish between components, in order to more clearly illustrate/explain the technical solution, but are not to be understood as indicating or implying a quantity of technical features indicated or an order of substantial significance, etc.
As shown in fig. 1 and 2, the anode sheet 1 of the present invention includes an anode current collector having a first segment 11 and a second segment 12 connected to each other, a first anode active layer 101 on a surface of the first segment 11, and a second anode active layer 102 on a surface of the second segment 12, the first anode active layer 101 containing a first anode active material including TiO 2 nanotubes.
According to the research of the invention, the first negative electrode active material can also comprise a graphite-based material, and the TiO 2 nano tube and the graphite-based material are used as the first negative electrode active material together, so that the low-temperature performance of the negative electrode sheet and the electrochemical device can be further improved. The graphite-based material is a material based on graphite, and includes, for example, graphite. In contrast, too high or too low a ratio of the TiO 2 nanotubes to the graphite-based material may affect the low temperature performance of the negative electrode sheet and the electrochemical device, such as low temperature discharge capacity, to some extent, and further research shows that the mass ratio of the titanium dioxide nanotubes to the graphite-based material in the first negative electrode active material may generally be (45-97): 5, e.g., 45:5, 50:5, 60:5, 70:5, 80:5, 90:5, 97:5, or any two ratio ranges therein.
In general, the mass content of TiO 2 nanotubes in the first anode active layer 101 is 2% to 10%, that is, the mass ratio of TiO 2 nanotubes is 2% to 10%, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or a range of any two of them, based on the total mass of the first anode active layer 101.
Specifically, the first anode active layer 101 contains a conductive agent, a binder, a dispersant, and the first anode active material, wherein the mass content of the first anode active material in the first anode active layer 101 is 95 to 98%, the mass content of the conductive agent is 0.3 to 0.6%, the mass content of the binder is 0.5 to 3%, and the mass content of the dispersant is 0.5 to 2%.
In addition, the second anode active layer 102 contains a second anode active material, which is typically different from the first anode active material, and does not include TiO 2 nanotubes (i.e., no TiO 2 nanotubes are contained in the second anode active layer 102). In some preferred embodiments, the second negative electrode active material includes a graphite-based material that is a graphite-based (major component) material, including, for example, graphite. Alternatively, the graphite-based materials in the first negative electrode active material and the second negative electrode active material may be the same or different, preferably the same, e.g., both graphite.
Specifically, the second anode active layer 102 includes a conductive agent, a binder, a dispersant, and the second anode active material, wherein the second anode active material has a mass content of 95% to 98%, the conductive agent has a mass content of 0.3% to 0.6%, the binder has a mass content of 0.5% to 3%, and the dispersant has a mass content of 0.5% to 2%.
Wherein the conductive agents in the first anode active layer 101 and the second anode active layer may be the same or different, the binder in the first anode active layer 101 and the second anode active layer 102 may be the same or different, and the dispersant in the first anode active layer 101 and the second anode active layer 102 may be the same or different. In some preferred embodiments, in the above-described first and second anode active layers 101 and 102, the conductive agent includes at least one of carbon black, carbon nanotubes, conductive graphite, and graphene, respectively, the binder includes at least one of polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, and Styrene Butadiene Rubber (SBR), and the dispersant includes at least one of carboxymethyl cellulose (CMC), respectively, which may include sodium carboxymethyl cellulose (CMC-Na) and/or lithium carboxymethyl cellulose (CMC-Li), for example, CMC-Na is used as the dispersant, but the conductive agent, binder, and dispersant used in the present invention are not limited thereto.
In the present invention, the negative electrode current collector has two surfaces, namely, one surface of the first section 11 is provided with the first negative electrode active layer 101, or both surfaces of the first section 11 are provided with the first negative electrode active layer 101, and the latter is generally preferable; the second negative electrode active layer 102 may be provided on one surface of the second segment 12, or the second negative electrode active layer 102 may be provided on both surfaces of the second segment 12, and the latter is generally preferable. In contrast, the first negative electrode active layer 101 is disposed on two surfaces of the first section 11, and the second negative electrode active layer 102 is disposed on two surfaces of the second section 12, which is beneficial to further improving performances such as energy density of the negative electrode sheet.
Furthermore, the first section 11 may also present a single-sided coating zone generally located at an end of the first section 11 remote from the second section 12, e.g., in some preferred embodiments, the first section 11 includes a connected first portion 111 and second portion 112, the second portion 112 being located between the first portion 111 and the second section 12; one surface of the first portion 111 is provided with the first anode active layer 101, the other surface of the first portion 111 is not provided with the first anode active layer 101 (the other surface of the first portion 111 is generally an empty foil area without a coating, the first portion 111 is a single-sided coating area), both surfaces of the second portion 112 are provided with the first anode active layer 101, and both surfaces of the second section 12 are provided with the second anode active layer 102. Wherein the ratio of the lengths of the first portion 111 and the second portion 112 in the direction from the first segment 11 to the second segment 12 (generally, the length direction of the negative electrode sheet) may be 1: (3-5). The negative electrode sheet 1 may particularly form a winding structure (as shown in fig. 2), and the first portion 111, the second portion 112, and the second segment 12 are sequentially distributed along the winding direction of the winding structure from inside to outside as the negative electrode of the winding type battery cell, so that it is advantageous to further optimize the characteristics such as low temperature performance of the winding type battery cell and the electrochemical device including the winding type battery cell.
In the present invention, the first and second segments 11 and 12 are disposed in order along the length direction of the negative electrode current collector, and in some embodiments, it is satisfied that a/b is (0.45 to 0.65) 1, a is the length of the first segment 11 in the direction from the first segment 11 to the second segment 12, and b is the sum of the length of the first segment 11 in the direction from the first segment 11 to the second segment 12 and the length of the second segment 12 in the direction from the first segment 11 to the second segment 12.
In general, the ratio of the length of the first anode active layer 101 of the first segment 11 to the length of the first anode active layer 101 of the second segment 12 in the direction from the first segment 11 to the second segment 12 is substantially equal to a/b (i.e., 0.45 to 0.65): 1) on the first surface a of the anode current collector, which is the surface of the first portion 111 provided with the first anode active material layer; the ratio of the length of the first anode active layer 101 of the first segment 11 to the length of the first anode active layer 101 of the second segment 12 in the direction from the first segment 11 to the second segment 12 is substantially equal to d/e, d being the length of the second portion 112 in the direction from the first segment 11 to the second segment 12, e being the sum of the length of the second portion 112 in the direction from the first segment 11 to the second segment 12 and the length of the second segment 12 in the direction from the first segment 11 to the second segment 12, d/e may be (0.4 to 0.6) 1, d/e being smaller than a/b, and C being the surface of the first portion 111 not provided with the first anode active layer 101.
In the present invention, the negative electrode tab 1 is provided with a negative electrode tab 13, and the negative electrode tab 13 is provided on the first section 11, specifically, may be provided on the surface of the first section 11 provided with the first negative electrode active layer 101. The number of the negative electrode tabs 13 is at least one, that is, one or more, and generally at least one of the negative electrode tabs 13 is disposed on the second portion 112, specifically, may be disposed on a first surface a of the second portion 112, where the first surface a is a surface of the first portion 111 provided with the first negative electrode active layer 101.
In the present invention, the negative electrode current collector includes, for example, copper foil, but is not limited thereto. The negative electrode tab 13 may be welded to the surface of the negative electrode current collector.
The negative electrode sheet 1 of the present invention may be produced by a method conventional in the art such as a coating method, for example, by mixing the negative electrode active material of the first negative electrode active layer 101, the conductive agent, the binder, the dispersant, and the first solvent to produce a first negative electrode slurry; mixing the anode active material, the conductive agent, the binder and the dispersing agent of the second anode active layer 102 with the first solvent to prepare a second anode slurry; the method comprises the steps of respectively coating a first negative electrode slurry and a second negative electrode slurry on a first section 11 and a second section 12 of a negative electrode current collector, sequentially drying, rolling and the like, respectively forming a first negative electrode active layer 101 on the first section 11, forming a second negative electrode active layer 102 on the second section 12, removing the coating at the position of a preset negative electrode tab, welding the negative electrode tab at the position, and then cutting the obtained base material according to the preset shape, the preset size and the like of the negative electrode tab 1 to obtain the negative electrode tab 1.
The electrochemical device of the present invention includes the above-described negative electrode sheet 1. The electrochemical device is, for example, a battery, and may be, in particular, a lithium ion battery.
In some embodiments, the negative electrode sheet 1 includes at least two first straight portions, and a first bending portion 14 connected between each two first straight portions, and the negative electrode sheet 1 is bent by the first bending portion 14 to form a coiled structure, where the first segment 11 and the second segment 12 are sequentially distributed along a coiling direction of the coiled structure from inside to outside (i.e., the first segment 11 is located at a center of the coiled structure). When the first segment 11 of the negative electrode sheet 1 includes the first portion 111 and the second portion 112, the first portion 111, the second portion 112, and the second segment 12 are sequentially distributed along the winding direction of the winding structure from inside to outside.
Typically, the first segment 11 includes m first straight portions, the second segment 12 includes n first straight portions, m and n are integers not less than 2, and n is not less than m. In some embodiments, in the winding direction of the wound structure from inside to outside, the first straight portion of the first section 11 of the negative electrode sheet 1 located at the outermost side of the wound structure is provided with negative electrode tabs 13, specifically, when the number of negative electrode tabs 13 on the negative electrode is 1, the negative electrode tabs 13 are disposed on the first straight portion of the first section 11 located at the outermost side of the wound structure, and when the number of negative electrode tabs 13 is two or more, at least one negative electrode tab 13 is disposed on the first straight portion of the first section 11 located at the outermost side of the wound structure.
Illustratively, m=4 (i.e., the first segment 11 includes four first straight portions), the number of the negative electrode tabs 13 is 1, and the negative electrode tabs 13 are disposed on the fourth first straight portion 1104 (as shown in fig. 2) in the winding direction of the winding structure from the first straight portion of the first segment 11 located at the innermost side of the winding structure being the first straight portion 1101; or m=8 (i.e., the first segment 11 includes 8 first straight portions), the number of the negative electrode tabs 13 is 1, and the negative electrode tabs 13 are disposed on the eighth first straight portion, from the first straight portion of the first segment 11 located at the innermost side of the wound structure being the first straight portion 1101. Wherein the sum of the number of first straight portions of the first segment 11 and the number of first straight portions of the second segment 12 is 16 (i.e., m+n=16).
In the present invention, the electrochemical device further includes a positive electrode sheet 2, where the positive electrode sheet 2 and the negative electrode sheet 1 are stacked and wound to form a winding structure, specifically, the positive electrode sheet 2 includes a positive electrode current collector and a positive electrode active layer, the positive electrode sheet 2 has at least two second straight portions, and a second bending portion 22 connected between every two second straight portions, the positive electrode sheet 2 is bent to form a winding structure by the second bending portion 22, the positive electrode sheet 2 is further provided with a positive electrode tab 23, the positive electrode tab 23 is disposed on the second straight portions, the second straight portions of the positive electrode sheet 2 located at the innermost side of the winding structure are the first second straight portions 21, and the positive electrode tab 23 may be disposed on the x second straight portions along the winding direction of the winding structure from inside to outside, and positive and negative electrode active layers are disposed on both surfaces of the x=2, for example, x=4 (as shown in fig. 2).
The positive electrode active layer includes a positive electrode active material including a lithium-containing positive electrode active material including, for example, at least one of Lithium Cobalt Oxide (LCO), nickel cobalt manganese ternary material (NCM), nickel cobalt aluminum ternary material (NCA), nickel cobalt manganese aluminum quaternary material (NCMA), lithium iron phosphate (LFP), lithium Manganese Phosphate (LMP), lithium Vanadium Phosphate (LVP), lithium Manganate (LMO), lithium-rich manganese group, a conductive agent including at least one of conductive carbon black, carbon nanotubes, conductive graphite, graphene, and a binder including at least one of polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinyl pyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, and styrene-butadiene rubber. The positive electrode current collector includes, for example, aluminum foil, but is not limited thereto.
The above electrochemical device further includes a separator 3 between the positive electrode sheet 2 and the negative electrode sheet 1, the separator 3 serving to space the positive electrode sheet 2 and the negative electrode sheet 1, which may be conventional separators in the art, to which the present invention is not particularly limited.
The electrochemical device of the present invention may be manufactured according to a conventional method in the art, for example, after stacking the positive electrode sheet 2, the separator 3, and the negative electrode sheet 1 in sequence, winding to form a winding type cell (or called winding core), and then performing the steps of packaging, baking, liquid injection, formation, secondary sealing, sorting, etc., to manufacture the electrochemical device, where the steps/steps are all conventional operations in the art, and will not be repeated.
For the purpose of promoting an understanding of the principles of the invention, reference will now be made in detail to specific examples, some but not all of which are illustrated in the accompanying drawings. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
In this embodiment, the electrochemical device is a wound lithium ion battery, which includes a wound cell including a positive electrode sheet 2, a separator 3, and a negative electrode sheet 1 stacked in order, wherein,
The negative electrode sheet 1 comprises a negative electrode current collector with a first section 11 and a second section 12 which are connected, a first negative electrode active layer 101 positioned on the surface of the first section 11, and a second negative electrode active layer 102 positioned on the surface of the second section 12, wherein the first section 11 consists of a first part 111 and a second part 112, and the second part 112 is positioned between the first part 111 and the second section 12;
The first negative electrode active layer 101 is arranged on one surface of the first part 111, the first negative electrode active layer 101 is not arranged on the other surface (namely, an empty foil area without a coating layer) of the first negative electrode active layer 101 is arranged on the front surface and the back surface of the second part 112, and the second negative electrode active layer 102 is arranged on the front surface and the back surface of the second section 12;
The total length of the anode active layer of the first surface a of the anode current collector is about 944±2mm (the length of the first anode active layer 101 of the first section 11 is about 531±2mm, and the length of the second anode active layer 102 of the second section 12 is about 413±2 mm) in the direction from the first section 11 to the second section 12 (i.e., the length direction of the anode current collector) before winding; the total length of the anode active layers of the second surface C of the anode current collector is about 822±2mm (the length of the first anode active layer 101 of the first segment 11 is about 409±2mm, and the length of the second anode active layer 102 of the second segment 12 is about 413±2 mm); wherein the length of the first portion 111 is about 122+ -2 mm, the length of the second portion 112 is about 409+ -2 mm, the length of the first section 11 is about 531+ -2 mm, and the length of the second section 12 is about 413+ -2 mm; the first surface a is a surface of the first portion 111 where the first anode active layer 101 is provided, and the second surface C is a surface of the first portion 111 where the first anode active layer 101 is not provided; further, the width of the negative electrode current collector is about 77.5±0.1mm;
In the winding type battery cell, the positive electrode plate 2, the diaphragm 3 and the negative electrode plate 1 are stacked and bent to form a winding type structure, the negative electrode plate 1 comprises 16 first straight parts and first bending parts 14 (the number of the first bending parts 14 is about 15) connected between every two first straight parts, the negative electrode plate 1 is bent through the first bending parts 14 to form a winding type structure, and the first part 111, the second part 112 and the second section 12 are sequentially distributed along the winding direction of the winding type structure from inside to outside;
The negative pole piece comprises a negative pole tab 13, the negative pole tab 13 is arranged on a first straight part of the first section 11, which is positioned at the outermost side of the winding type structure, along the winding direction from the inside to the outside of the winding type structure, and the first straight part of the first section 11, which is positioned at the innermost side of the winding type structure, is a first straight part 1101, and the first straight part of the first section 11, which is positioned at the outermost side of the winding type structure, is an eighth first straight part along the winding direction from the inside to the outside of the winding type structure;
The positive plate 2 comprises a positive current collector and a positive active layer, the positive plate 2 is provided with a plurality of second straight parts and a second bending part 22 connected between every two second straight parts, the positive plate 2 is bent to form a winding structure through the second bending part 22, the positive plate 2 is also provided with a positive tab 23, the positive tab 23 is arranged on the second straight parts, the second straight part of the positive plate 2 positioned at the innermost side of the winding structure is counted as a first second straight part 21, and the positive tab 23 is arranged on the 4 th second straight part along the winding direction of the winding structure from inside to outside.
The preparation process of the positive plate, the negative plate and the lithium ion battery in this embodiment is as follows:
(1) Preparation of positive plate
Adding lithium cobaltate, carbon black and polyvinylidene fluoride into a stirring tank according to the mass ratio of 97.2:1.5:1.3, adding N-methyl pyrrolidone (NMP) into the stirring tank as a solvent, fully stirring, and then sieving the mixture with a 200-mesh sieve to prepare anode slurry with the solid content of 70-75wt%; coating positive electrode slurry on the front and back surfaces of an aluminum foil (namely a positive electrode current collector) by using a coating machine, drying at 120 ℃, rolling, forming positive electrode active material layers on the front and back surfaces of the aluminum foil, removing the coating at the position of a preset positive electrode lug, welding the positive electrode lug at the position, and cutting the obtained positive electrode plate base material according to the preset shape, the preset size and other parameters of the positive electrode plate to obtain the positive electrode plate;
(2) Preparation of negative electrode sheet
Adding graphite, tiO 2 nano-tubes, carbon black, SBR and CMC into a stirring tank according to the mass ratio of 96.9:5:0.5:1.3:1.3, adding deionized water into the stirring tank, fully stirring, and then passing through a 200-mesh screen to prepare a first negative electrode slurry with the solid content of 40-45 wt%;
adding graphite, carbon black, SBR and CMC into a stirring tank according to the mass ratio of 96.9:0.5:1.3:1.3, adding deionized water into the stirring tank, fully stirring, and then sieving the mixture with a 200-mesh sieve to prepare second negative electrode slurry with the solid content of 40-45 wt%;
Sequentially coating a first negative electrode slurry on a preset area of a first section of a copper foil (namely a negative electrode current collector), coating a second negative electrode slurry on a preset area of a second section of the copper foil, drying at 120 ℃, rolling, respectively forming a first negative electrode active layer on the first section and a second negative electrode active layer on the second section, removing a coating at the position of a preset negative electrode tab, welding the negative electrode tab at the position, and then cutting the obtained base material according to parameters such as the preset shape and the preset size of the negative electrode tab 1 to obtain a negative electrode tab;
(3) Preparation of lithium ion batteries
And sequentially stacking the positive plate, the diaphragm and the negative plate, winding to form a winding type battery cell, and then packaging, baking, injecting liquid, forming, secondarily sealing, sorting and the like to obtain the lithium ion battery.
Referring to the preparation process of example 1, positive electrode sheets, negative electrode sheets and lithium ion batteries of examples 2 to 4 and comparative example 1 were prepared, and examples 2 to 4, comparative example 1 and example 1 were different in that the mass ratio of graphite to TiO 2 nanotubes for preparing the first negative electrode slurry was different, specifically, see table 1, and the other conditions were substantially the same as in example 1.
The lithium ion batteries of examples 1 to 4 and comparative example 1 were subjected to a normal temperature cycle test by a conventional method in the art, and the test procedure is briefly described as follows:
charging a lithium ion battery to an upper limit voltage at 0 ℃ at 2C multiplying power, then charging at constant voltage, wherein the cut-off current is 0.05C, discharging the battery to 3V at 0.5C multiplying power after charging, and measuring the capacity retention rate of the battery after 500 circles (500T) of circulation at 0 ℃ by taking the battery as a circle of circulation, wherein the result is shown in Table 1;
The lithium ion batteries of examples 1 to 4 and comparative example 1 were subjected to a low-temperature discharge test, and the test procedure was as follows:
(1) Charging the battery to the upper limit voltage at the rate of 0.5C at normal temperature, and then charging at a constant voltage, wherein the cut-off current is 0.05C; the battery was allowed to stand at-10℃for 4H and discharged to 3V at a rate of 0.4C, and the discharge capacity of the battery at-10℃and 0.4C was measured as shown in Table 1;
(2) Charging the battery to the upper limit voltage at the rate of 0.5C at normal temperature, and then charging at a constant voltage, wherein the cut-off current is 0.05C; the discharge capacity of the battery at-20℃and 0.2C rate was measured by discharging the battery at-20℃for 4H at 0.2C rate to 3V, as shown in Table 1.
Table 1 results of performance testing of lithium ion batteries of examples and comparative examples
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. An electrochemical device comprising a negative electrode sheet; the negative electrode sheet comprises a negative electrode current collector with a first section and a second section which are connected, a first negative electrode active layer positioned on the surface of the first section and a second negative electrode active layer positioned on the surface of the second section, wherein the first negative electrode active layer comprises a first negative electrode active substance, and the first negative electrode active substance comprises titanium dioxide nanotubes; the negative electrode plate is provided with a negative electrode lug, and the negative electrode lug is arranged on the first section;
1, a is the length of the first section in the direction from the first section to the second section, and b is the sum of the length of the first section in the direction from the first section to the second section and the length of the second section in the direction from the first section to the second section; the negative plate comprises at least two first straight parts and first bending parts connected between every two first straight parts, the negative plate is bent through the first bending parts to form a winding structure,
The first section and the second section are distributed in sequence along the winding direction of the winding structure from inside to outside;
Along the winding direction of the winding structure from inside to outside, a first straight part of the first section of the negative electrode sheet, which is positioned at the outermost side of the winding structure, is provided with a negative electrode tab;
The first section comprises a first portion and a second portion connected, the second portion being located between the first portion and the second section;
the first negative electrode active layer is arranged on one surface of the first part, the first negative electrode active layer is arranged on two surfaces of the second part, and the second negative electrode active layer is arranged on two surfaces of the second section;
The ratio of the lengths of the first portion and the second portion in the direction from the first section to the second section is 1: (3-5).
2. The electrochemical device according to claim 1, wherein,
The first negative electrode active material further includes a graphite-based material; and/or the number of the groups of groups,
The second anode active layer includes a second anode active material including a graphite-based material.
3. The electrochemical device according to claim 2, wherein in the first negative electrode active material, a mass ratio of the titanium dioxide nanotube to the graphite-based material is (45 to 97): 5.
4. The electrochemical device according to any one of claims 1 to 3, wherein the mass content of the titania nanotubes in the first anode active layer is 2% to 10%.
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