CN114005954A - Negative electrode sheet and electrochemical device - Google Patents
Negative electrode sheet and electrochemical device Download PDFInfo
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- CN114005954A CN114005954A CN202111260322.6A CN202111260322A CN114005954A CN 114005954 A CN114005954 A CN 114005954A CN 202111260322 A CN202111260322 A CN 202111260322A CN 114005954 A CN114005954 A CN 114005954A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002071 nanotube Substances 0.000 claims abstract description 20
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 8
- 238000004804 winding Methods 0.000 claims description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000010439 graphite Substances 0.000 claims description 24
- 229910002804 graphite Inorganic materials 0.000 claims description 24
- 239000007773 negative electrode material Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 239000006183 anode active material Substances 0.000 claims description 5
- 239000013543 active substance Substances 0.000 abstract 2
- 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
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- 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
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
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- 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
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
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- 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
Abstract
The invention provides a negative plate and an electrochemical device, wherein the negative plate comprises a negative current collector with a first section and a second section which are connected, a first negative active layer positioned on the surface of the first section, and a second negative active layer positioned on the surface of the second section, wherein the first negative active layer comprises a first negative active substance, and the first negative active substance comprises a titanium dioxide nanotube. The invention can improve the low-temperature performance of the negative 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, portable power sources have been widely used in various applications, and the use conditions of various electronic devices have gradually increased requirements for the performance of electrochemical devices such as lithium ion batteries, especially in low-temperature environments such as high altitude areas and high altitude areas. At present, electrochemical devices such as lithium ion batteries and the like have poor low-temperature performance, show poor specific discharge capacity at low temperature, and even are difficult to perform normal charge and discharge, and the reasons for the poor low-temperature performance mainly include the following aspects: (1) the electrolyte has low viscosity at low temperature, and the ionic conductivity is obviously reduced; (2) the compatibility of the electrolyte with a negative electrode and a diaphragm is poor at low temperature, the normal transmission of lithium ions is influenced, and the diffusion capacity of the lithium ions in the active material is reduced; (3) lithium is easy to be separated out at low temperature. Therefore, how to improve the low-temperature performance of the electrochemical device is an important issue for 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 in the prior art.
In one aspect of the invention, a negative plate is provided, which includes a negative current collector having a first segment and a second segment connected to each other, and a first negative active layer on a surface of the first segment and a second negative active layer on a surface of the second segment, wherein the first negative active layer includes a first negative active material, and the first negative active material includes 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, a mass ratio of the titanium dioxide nanotubes 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, a mass content of the titanium dioxide nanotube is 2% to 10%.
According to one embodiment of the present invention, a/b is (0.45-0.65) 1, a is the length of the first segment in the direction from the first segment to the second segment, and b is the sum of the length of the first segment in the direction from the first segment to the second segment and the length of the second segment in the 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 portion is provided with the first negative active layer, two surfaces of the second portion are provided with the first negative active layer, and two surfaces of the second segment are provided with the second negative active layer.
According to an embodiment of the present invention, the negative electrode tab is disposed on the first segment.
In another aspect of the present invention, there is provided an electrochemical device comprising the above negative electrode sheet.
According to an embodiment of the present invention, the negative electrode sheet includes at least two first straight portions and a first bending portion connected between every two first straight portions, the negative electrode sheet is bent by the first bending portion to form a winding structure, and the first segment and the second segment are sequentially distributed along a winding direction from inside to outside of the winding structure.
According to an embodiment of the present invention, a negative electrode tab is provided on a first straight portion of the first segment of the negative electrode sheet located on the outermost side of the winding structure along a winding direction of the winding structure from inside to outside.
In the invention, the negative electrode sheet is sectionally provided with the negative electrode active layer, and the negative electrode active layer is arranged on the negative electrode sheetTitanium dioxide (TiO) is introduced into the negative electrode active layer (i.e., the first negative electrode active layer) of the first stage in (b)2) The nanotube can improve the low-temperature performance of the negative plate and the electrochemical device adopting the negative plate, inhibit the phenomenon of low-temperature lithium precipitation and improve the low-temperature discharge capacity of the negative plate, and is specifically represented as follows: the discharge capacity at minus 10 ℃ and 0.4C rate can reach more than 84 percent, and the discharge capacity at minus 20 ℃ and 0.2C rate can reach more than 70 percent. According to the research analysis of the inventors, TiO2The nanotube has small diameter, short ion (such as lithium ion) diffusion path, large specific surface area and good dynamic performance; at the same time, TiO2The nano tube is used as a negative electrode active material of the lithium ion battery, has small volume strain (less than 4 percent) and higher potential relative to lithium, and can avoid the formation of lithium dendrite, thereby improving the phenomenon of low-temperature lithium precipitation; furthermore, TiO2The lithium intercalation potential (1.5V) of the nanotube is higher than that of negative active materials such as graphite-based materials, lithium is firstly intercalated in the electrochemical device during charging, and ohmic heat is generated due to current circulation in the lithium intercalation process, so that the temperature of a battery core of the electrochemical device is increased, the viscosity of the electrolyte is improved, the compatibility of the electrolyte with a negative plate and a diaphragm is improved, the ionic 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 structural diagram of a negative electrode sheet according to an embodiment of the invention;
fig. 2 is a schematic diagram of a winding type cell structure according to an embodiment of the invention.
Description of reference numerals:
1: a negative plate;
2: a positive plate;
3: a diaphragm;
11: a first stage;
12: a second stage;
13: a negative electrode tab;
14: a first bent portion;
21: a first and second straight portion;
22: a second bent portion;
23: a positive electrode tab;
101: a first negative electrode active layer;
102: a second negative electrode active layer;
111: a first part;
112: a second section;
1101: a first straight portion;
1104: a fourth first straight portion;
a: a first surface of a negative current collector;
c: a second surface of the negative current collector.
Detailed Description
The present invention is described in further detail below in order to enable those skilled in the art to better understand the aspects of the present invention. The following detailed description is merely illustrative of the principles and features of the present invention, and the examples are intended to be illustrative of the invention and not limiting of the scope of the invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention. In the description of the present invention, the terms "first", "second", and the like are used for descriptive purposes only, for example, to distinguish various components for clarity of explanation/explanation of the technical solution, and are not to be construed as indicating or implying any number of technical features or order of significance.
As shown in fig. 1 and 2, the negative electrode sheet 1 of the present invention includes a negative electrode collector having a first segment 11 and a second segment 12 connected to each other, and a first negative electrode active layer 101 on a surface of the first segment 11 and a second negative electrode active layer 102 on a surface of the second segment 12, the first negative electrode active layer 101 including a first negative electrode active material including TiO2A nanotube.
According to the research of the present invention, the first negative active material may further include a graphite-based material, in the form of TiO2The nanotube and the graphite-based material are jointly used as the first negative active material, which is beneficial to further improving the low temperature of the negative plate and the electrochemical deviceAnd (4) performance. The graphite-based material is a material using graphite as a matrix, and includes graphite, for example. In contrast, TiO2The low-temperature performance such as the low-temperature discharge capacity of the negative electrode plate and the electrochemical device can be influenced to a certain extent by too high or too low proportion of the nanotube and the graphite-based material, and through further research, the mass ratio of the titanium dioxide nanotube to the graphite-based material in the first negative electrode active material can be generally (45-97): 5, e.g., 45:5, 50:5, 60:5, 70:5, 80:5, 90:5, 97:5, or a range consisting of any two ratios thereof.
In general, in the first negative electrode active layer 101, TiO2The mass content of the nanotube is 2% to 10%, that is, TiO based on the total mass of the first negative electrode active layer 1012The mass ratio of the nanotubes is 2% to 10%, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or any two of these ranges.
Specifically, the first negative electrode active layer 101 includes a conductive agent, a binder, a dispersant, and the first negative electrode active material, and in the first negative electrode active layer 101, the mass content of the first negative electrode active material 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 generally different from the first anode active material and does not include TiO2Nanotubes (i.e., no TiO is included in the second negative active layer 102)2Nanotubes). In some preferred embodiments, the second negative electrode active material includes a graphite-based material that is a material having graphite as a matrix (main component), and includes graphite, for example. Alternatively, the graphite-based material in the first and second anode active materials may be the same or different, preferably the same, e.g. both graphite.
Specifically, the second negative electrode active layer 102 includes a conductive agent, a binder, a dispersant, and the above-described second negative electrode active material, and in the second active layer, the mass content of the first negative electrode active material 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%.
Here, the conductive agent in the first and second anode active layers 101 and 102 may be the same or different, the binder in the first and second anode active layers 101 and 102 may be the same or different, and the dispersant in the first and second anode active layers 101 and 102 may be the same or different. In some preferred embodiments, in the first negative electrode active layer 101 and the second negative electrode active layer 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, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, and Styrene Butadiene Rubber (SBR), the dispersant includes carboxymethyl cellulose (CMC), the carboxymethyl cellulose 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 invention, the negative current collector has two surfaces, wherein one surface of the first section 11 is provided with the first negative active layer 101, or both surfaces of the first section 11 are provided with the first negative active layer 101, and the latter is generally preferred; further, one surface of the second segment 12 may be provided with the second negative electrode active layer 102, or both surfaces of the second segment 12 may be provided with the second negative electrode active layer 102, and the latter is generally preferred. In contrast, the first negative active layer 101 is disposed on each of the two surfaces of the first section 11, and the second negative active layer 102 is disposed on each of the two surfaces of the second section 12, which is beneficial to further improving the performance of the negative plate, such as energy density.
In addition, the first section 11 may also present a single facer coating region that is generally located at the end of the first section 11 distal from the second section 12, e.g., in some preferred embodiments, the first section 11 includes a first portion 111 and a second portion 112 that are connected, 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 a first negative electrode active layer 101, the other surface of the first portion 111 is not provided with the first negative electrode active layer 101 (the other surface of the first portion 111 is generally an uncoated empty foil region, and the first portion 111 is a single-sided coating region), both surfaces of the second portion 112 are provided with the first negative electrode active layer 101, and both surfaces of the second segment 12 are provided with the second negative electrode active layers 102. 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 as a negative electrode of the winding type battery cell, the first portion 111, the second portion 112, and the second segment 12 are sequentially distributed along a winding direction from inside to outside of the winding structure, which is beneficial to further optimizing characteristics of the winding type battery cell and an electrochemical device including the winding type battery cell, such as low-temperature performance.
In the present invention, the first section 11 and the second section 12 are sequentially disposed along the length direction of the negative electrode collector, and in some embodiments, a/b is (0.45-0.65): 1, a is the length of the first section 11 in the direction from the first section 11 to the second section 12, and b is the sum of the length of the first section 11 in the direction from the first section 11 to the second section 12 and the length of the second section 12 in the direction from the first section 11 to the second section 12.
In general, on the first surface a of the negative electrode collector, the ratio of the length of the first negative electrode active layer 101 of the first segment 11 to the length of the first negative electrode 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), and the first surface a is the surface of the first portion 111 on which the first negative electrode active material layer is provided; on the second surface C of the negative electrode collector, the ratio of the length of the first negative electrode active layer 101 of the first section 11 to the length of the first negative electrode active layer 101 of the second section 12 in the direction from the first section 11 to the second section 12 is substantially equal to d/e, d is the length of the second portion 112 in the direction from the first section 11 to the second section 12, e is the sum of the length of the second portion 112 in the direction from the first section 11 to the second section 12 and the length of the second section 12 in the direction from the first section 11 to the second section 12, d/e may be (0.4-0.6): 1, and d/e is less than a/b, and the second surface C is a surface of the first portion 111 not provided with the first negative electrode active layer 101.
In the present invention, the negative electrode tab 13 is disposed on the first segment 11, and the negative electrode tab 13 may be disposed on the surface of the first segment 11 on which the first negative electrode active layer 101 is disposed. 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, and specifically, may be disposed on the first surface a of the second portion 112, where the first surface a is a surface of the first portion 111 on which the first negative electrode active layer 101 is disposed.
In the present invention, the negative electrode current collector includes, for example, a 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 manufactured by a conventional method in the art, such as a coating method, for example, mixing the negative electrode active material, the conductive agent, the binder, and the dispersant of the first negative electrode active layer 101 with a first solvent to prepare a first negative electrode slurry; mixing the negative electrode active material, the conductive agent, the binder, the dispersant of the second negative electrode active layer 102 with the first solvent to prepare a second negative electrode slurry; respectively coating the first negative electrode slurry and the 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 a coating at a preset negative electrode lug position, welding a negative electrode lug at the position, and then cutting the obtained substrate according to parameters such as the preset shape, the size and the like of the negative electrode plate 1 to obtain the negative electrode plate 1.
The electrochemical device of the present invention includes the above negative electrode sheet 1. The electrochemical device is, for example, a battery, and may be, specifically, a lithium ion battery.
In some embodiments, the negative electrode sheet 1 includes at least two first straight portions and a first bent portion 14 connected between every two first straight portions, the negative electrode sheet 1 is bent by the first bent portion 14 to form a winding structure, and the first segment 11 and the second segment 12 are sequentially distributed along a winding direction of the winding structure from inside to outside (i.e. the first segment 11 is located at the center of the winding 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 from the inside to the outside of the winding structure.
Generally, 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 winding structure from inside to outside, a first straight portion of the first segment 11 of the negative electrode sheet 1 located at the outermost side of the winding structure is provided with a negative electrode tab 13, specifically, when the number of the negative electrode tabs 13 on the negative electrode is 1, the negative electrode tab 13 is provided on a first straight portion of the first segment 11 located at the outermost side of the winding structure, and when the number of the negative electrode tabs 13 is two or more, at least one negative electrode tab 13 is provided on a first straight portion of the first segment 11 located at the outermost side of the winding structure.
Exemplarily, m is 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) along the winding direction from the inside to the outside of the winding structure from the first straight portion 1101, which is the innermost first straight portion of the winding structure of the first segment 11; alternatively, m is 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 winding structure as the first straight portion 1101. The sum of the number of the first straight portions of the first segment 11 and the number of the first straight portions of the second segment 12 is 16 (i.e., m + n is 16).
In the invention, the electrochemical device also comprises a positive plate 2, the positive plate 2 and a negative plate 1 are laminated and wound to form a winding structure, specifically, the positive plate 2 comprises a positive current collector and a positive active layer, the positive plate 2 has at least two second straight parts and a second bending part 22 connected between every two second straight parts, the positive plate 2 is bent into a winding structure through the second bending part 22, the positive plate 2 is also provided with a positive pole tab 23, the positive pole tab 23 is arranged on the second straight part, the positive pole tab 23 can be arranged on the x-th second straight part along the winding direction from inside to outside of the winding structure from the first second straight part 21 which is the second straight part of the positive plate 2 which is positioned at the innermost side of the winding structure, positive electrode active layers are arranged on both the front surface and the back surface of the xth second straight part, wherein x is larger than or equal to 2, for example, x is larger than or equal to 4 (as shown in fig. 2).
The positive active layer comprises a positive active material, a conductive agent and a binder, the positive active material comprises a lithium-containing positive active material, for example, the conductive material may include 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), and lithium rich manganese base, the conductive agent may include at least one of conductive carbon black, carbon nanotubes, conductive graphite, and graphene, and the binder may include at least one of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, and styrene butadiene rubber. The positive electrode collector includes, for example, an aluminum foil, but is not limited thereto.
The above electrochemical device further includes a separator 3 between the positive electrode tab 2 and the negative electrode tab 1, the separator 3 being used to separate the positive electrode tab 2 and the negative electrode tab 1, which may be a separator conventional in the art, and the present invention is not particularly limited thereto.
The electrochemical device of the present invention can be manufactured according to the conventional method in the art, for example, the positive electrode sheet 2, the separator 3, and the negative electrode sheet 1 are sequentially stacked and wound to form a wound electrical core (or called a "jelly roll"), and then the electrochemical device is manufactured through the processes of packaging, baking, injecting liquid, forming, secondary sealing, sorting, etc., and these steps/processes are all conventional operations in the art and are not described in detail.
To make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In this embodiment, the electrochemical device is a winding type lithium ion battery, which includes a winding type electric core, the winding type electric core includes a positive plate 2, a diaphragm 3 and a negative plate 1, which are sequentially stacked, wherein,
the negative electrode sheet 1 comprises a negative electrode 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 is composed 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;
one surface of the first part 111 is provided with a first negative electrode active layer 101, the other surface is not provided with the first negative electrode active layer 101 (namely, an empty foil area without a coating), the front surface and the back surface of the second part 112 are both provided with the first negative electrode active layer 101, and the front surface and the back surface of the second section 12 are both provided with the second negative electrode active layer 102;
the total length of the negative active layer of the first surface a of the negative current collector is about 944 ± 2mm in the direction from the first segment 11 to the second segment 12 before winding (i.e., the length direction of the negative current collector) (the length of the first negative active layer 101 of the first segment 11 is about 531 ± 2mm, and the length of the second negative active layer 102 of the second segment 12 is about 413 ± 2 mm); the total length of the negative active layer of the second surface C of the negative current collector is about 822 ± 2mm (the length of the first negative active layer 101 of the first segment 11 is about 409 ± 2mm, and the length of the second negative active layer 102 of the second segment 12 is about 413 ± 2 mm); wherein, the length of the first part 111 is about 122 + -2 mm, the length of the second part 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 on which the first negative electrode active layer 101 is disposed, and the second surface C is a surface of the first portion 111 on which the first negative electrode active layer 101 is not disposed; further, the width of the negative electrode current collector was about 77.5 ± 0.1 mm;
in the winding type battery cell, the positive plate 2, the diaphragm 3 and the negative plate 1 are stacked and bent to form a winding type structure, the negative plate 1 comprises 16 first straight parts and first bent parts 14 (the number of the first bent parts 14 is about 15) connected between every two first straight parts, the negative plate 1 is bent to form the winding type structure through the first bent parts 14, 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 positioned at the outermost side of the winding structure along the winding direction of the winding structure from inside to outside, and the first straight part positioned at the outermost side of the winding structure is an eighth first straight part along the winding direction of the winding structure from inside to outside from the first straight part of the first section 11 positioned at the innermost side of the winding structure to a first straight part 1101;
positive plate 2 includes anodal mass flow body and anodal active layer, this positive plate 2 has the straight portion of a plurality of seconds, and connect the second kink 22 between per two straight portions of second, positive plate 2 forms coiling formula structure through the bending of second kink 22, this positive plate 2 still is equipped with anodal utmost point ear 23, anodal utmost point ear 23 sets up in the straight portion of second, it calculates for the straight portion 21 of first second to be located the straight portion of the most inboard second of coiling formula structure for anodal piece 2, along the coiling formula structure by interior and outer coiling direction, anodal utmost point ear 23 sets up in the straight portion of 4 th second.
The preparation processes of the positive plate, the negative plate and the lithium ion battery in the embodiment are 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-methylpyrrolidone (NMP) serving as a solvent, fully stirring, and then screening by a 200-mesh screen to prepare anode slurry with the solid content of 70-75 wt%; coating the positive electrode slurry on the front surface and the back surface of an aluminum foil (namely a positive electrode current collector) by using a coating machine, drying at the temperature of 120 ℃, rolling, forming positive electrode active material layers on the front surface and the back surface of the aluminum foil, removing a coating at a preset positive electrode tab position, welding a positive electrode tab at the position, and then cutting the obtained positive electrode sheet substrate according to parameters such as the preset shape, the preset size and the like of the positive electrode sheet to obtain the positive electrode sheet;
(2) preparation of negative plate
Mixing graphite and TiO2Adding the nanotube, the carbon black, the SBR and the CMC into a stirring tank according to a mass ratio of 96.9:5:0.5:1.3:1.3, adding deionized water into the stirring tank, fully stirring, and then screening by a 200-mesh screen to prepare first negative electrode slurry with a solid content of 40-45 wt%;
adding graphite, carbon black, SBR and CMC into a stirring tank according to a mass ratio of 96.9:0.5:1.3:1.3, adding deionized water into the stirring tank, fully stirring, and then sieving by a 200-mesh sieve to prepare second negative electrode slurry with a solid content of 40-45 wt%;
sequentially coating first negative electrode slurry on a preset area of a first section of a copper foil (namely a negative electrode current collector) and coating second negative electrode slurry on a preset area of a second section of the copper foil, drying at the temperature of 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 lug, welding the negative electrode lug at the position, and then cutting the obtained base material according to the preset parameters of shape, size and the like of a negative electrode sheet 1 to prepare the negative electrode sheet;
(3) preparation of lithium ion battery
And sequentially stacking the positive plate, the diaphragm and the negative plate, winding to form a winding type battery core, and then carrying out processes of packaging, baking, liquid injection, formation, secondary sealing, sorting and the like to obtain the lithium ion battery.
With reference to the preparation process of example 1, the positive electrode sheet, the negative electrode sheet and the lithium ion battery of examples 2 to 4 and comparative example 1 were prepared, and examples 2 to 4 and comparative example 1 were different from example 1 in that graphite and TiO of the first negative electrode slurry were prepared2The mass ratio of the nanotubes was varied, as shown in 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 the lithium ion battery to an upper limit voltage at a rate of 2C at 0 ℃, then charging at a constant voltage, stopping current at 0.05C, discharging the battery to 3V at a rate of 0.5C after the charging is finished, and measuring the capacity retention rate of the battery after 500 cycles (500T) at 0 ℃ in a cycle, wherein the results are 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 in the following procedure:
(1) charging the battery to an upper limit voltage at a rate of 0.5C at normal temperature, and then performing constant-voltage charging with a cutoff current of 0.05C; standing the battery at-10 deg.C for 4H, discharging at 0.4C rate to 3V, and measuring the discharge capacity of the battery at-10 deg.C and 0.4C rate as shown in Table 1;
(2) charging the battery to an upper limit voltage at a rate of 0.5C at normal temperature, and then performing constant-voltage charging with a cutoff current of 0.05C; the cell was left to stand at-20 ℃ for 4H and discharged to 3V at 0.2C rate, and the discharge capacity of the cell at-20 ℃ and 0.2C rate was measured and shown in Table 1.
TABLE 1 Performance test results for each of the examples and comparative examples lithium ion batteries
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The negative plate is characterized by comprising a negative current collector with a first section and a second section which are connected, a first negative active layer positioned on the surface of the first section, and a second negative active layer positioned on the surface of the second section, wherein the first negative active layer contains a first negative active material, and the first negative active material comprises titanium dioxide nanotubes.
2. Negative electrode sheet according to claim 1,
the first negative electrode active material further includes a graphite-based material; and/or the presence of a gas in the gas,
the second anode active layer includes a second anode active material including a graphite-based material.
3. The negative electrode sheet according to claim 2, wherein the mass ratio of the titanium dioxide nanotubes to the graphite-based material in the first negative electrode active material is (45-97): 5.
4. the negative electrode sheet according to any one of claims 1 to 3, wherein the titanium dioxide nanotubes are present in the first negative electrode active layer in an amount of 2 to 10% by mass.
5. The negative electrode sheet according to claim 1, wherein a/b is (0.45-0.65): 1, a is the length of the first segment in the direction from the first segment to the second segment, and b is the sum of the length of the first segment in the direction from the first segment to the second segment and the length of the second segment in the direction from the first segment to the second segment.
6. The negative plate of claim 1 or 5, wherein the first segment comprises a first portion and a second portion connected, the second portion being located between the first portion and the second segment;
one surface of the first portion is provided with the first negative active layer, two surfaces of the second portion are provided with the first negative active layer, and two surfaces of the second segment are provided with the second negative active layer.
7. A negative electrode sheet according to claim 1, wherein the negative electrode sheet is provided with a negative electrode tab disposed on the first segment.
8. An electrochemical device comprising the negative electrode sheet according to any one of claims 1 to 7.
9. The electrochemical device according to claim 8, wherein the negative electrode sheet comprises at least two first straight portions and a first bent portion connected between every two first straight portions, the negative electrode sheet is bent by the first bent portions to form a wound structure, and the first segment and the second segment are sequentially distributed along a winding direction from inside to outside of the wound structure.
10. The electrochemical device according to claim 9, wherein a negative electrode tab is provided on a first straight portion of the first segment of the negative electrode sheet located at the outermost side of the wound structure in a winding direction of the wound structure from inside to outside.
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