CN115832242A - Negative pole piece and preparation method thereof, secondary battery, battery module, battery pack and electric device - Google Patents
Negative pole piece and preparation method thereof, secondary battery, battery module, battery pack and electric device Download PDFInfo
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- CN115832242A CN115832242A CN202210846140.5A CN202210846140A CN115832242A CN 115832242 A CN115832242 A CN 115832242A CN 202210846140 A CN202210846140 A CN 202210846140A CN 115832242 A CN115832242 A CN 115832242A
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- negative electrode
- carbon material
- negative
- composite carbon
- battery
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Images
Classifications
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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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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a negative pole piece, include: a negative current collector, a negative active material layer, and a negative protective layer. A negative active material layer is disposed on at least one surface of the negative current collector. The negative electrode protective layer is arranged on the surface of the negative electrode active material layer, which is far away from the negative electrode current collector; the negative electrode protection layer includes a composite carbon material; the composite carbon material comprises MXene material and three-dimensional inorganic carbon material, wherein the three-dimensional inorganic carbon material contains metal oxide. According to the negative pole piece, the negative pole protective layer containing the specific composite carbon material is arranged, the composite carbon material has a two-dimensional/three-dimensional composite structure and high lithium affinity, lithium precipitation on the surface of the negative pole piece can be reduced, and the secondary battery has good cycle performance.
Description
Technical Field
The application relates to the technical field of secondary batteries, in particular to a negative pole piece and a preparation method thereof, a secondary battery, a battery module, a battery pack and an electric device.
Background
A lithium ion battery is a secondary battery that operates by movement of lithium ions between a positive electrode and a negative electrode. During charging and discharging, li + Intercalation and deintercalation to and from two electrodes: upon charging, li + The lithium ion battery is extracted from the positive electrode and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge. In the charging and discharging process, the active lithium loss of the lithium ion battery not only affects the capacity of the secondary battery, but also causes the deterioration of the negative pole piece and affects the cycle performance.
Disclosure of Invention
Based on the above problems, the present application provides a negative electrode sheet, a method for manufacturing the negative electrode sheet, a secondary battery, a battery module, a battery pack, and an electric device, which can improve cycle performance of the secondary battery.
In one aspect of the present application, there is provided a negative electrode tab, including:
a negative current collector;
a negative electrode active material layer disposed on at least one surface of the negative electrode current collector; and
the negative electrode protective layer is arranged on the surface of the negative electrode active material layer, which is far away from the negative electrode current collector; the negative electrode protection layer includes a composite carbon material; the composite carbon material comprises an MXene material and a three-dimensional inorganic carbon material, wherein the three-dimensional inorganic carbon material contains a metal oxide.
According to the negative pole piece, the negative pole protective layer containing the specific composite carbon material is arranged, the composite carbon material has a two-dimensional/three-dimensional composite structure and high lithium affinity, lithium precipitation on the surface of the negative pole piece can be reduced, and the secondary battery has good cycle performance.
In some of these embodiments, the MXene material comprises Ti 3 C 2 T x 、Ti 4 C 3 Tx、Ti 2 CT x 、V 2 CT x And Nb 2 CT x At least one of (1), wherein T x Functional group representing MXene Material, T x comprises-OH; alternatively, T x Further comprising at least one of = O, -F, and-Cl.
In some embodiments, the three-dimensional inorganic carbon material contains a carboxyl group, and the Mxene material is linked to the three-dimensional inorganic carbon material via an ester bond. The Mxene material and the three-dimensional inorganic carbon material are connected through ester bond covalent bonds, a stable two-dimensional/three-dimensional composite structure is formed in the negative electrode protection layer, lithium ion transmission can be improved, lithium precipitation on the surface of a negative electrode pole piece is avoided, and the cycle performance of the secondary battery is better.
In some of these embodiments, the composite carbon material has a specific surface area of 26m 2 /g～67m 2 G, optionally 26.92m 2 /g～66.04m 2 /g。
In some of these embodiments, the composite carbon material has a pore size of 5nm to 21nm, optionally 5.2nm to 20.1nm.
The composite carbon material has a high specific surface area and a rich pore diameter structure, is beneficial to improving lithium ion transmission, can fix lithium dendrites and other dead lithium in a negative electrode protective layer, and avoids the problems of pulverization and expansion of a negative electrode plate and the like caused by lithium dendrites and other dead lithium.
In some of these embodiments, the metal oxide comprises TiO 2 、ZnO、Fe 3 O 4 、Cr 2 O 3 、ZrO 2 And CuO;
optionally, the metal oxide is TiO 2 。
The metal oxide has better lithium affinity, and can improve the wettability of the negative pole piece to lithium ions, thereby improving the transmission of the lithium ions and reducing the internal resistance of the secondary battery.
In some embodiments, in the negative electrode protection layer, the mass percentage of the composite carbon material is 90% to 98%; optionally, in the negative electrode protection layer, the mass percentage content of the composite carbon material is 96% to 97.5%. The mass content of the composite carbon material in the negative electrode protective layer is in the range, the surface lithium precipitation of the negative electrode pole piece can be effectively reduced, and the secondary battery has good cycle performance.
In some embodiments, the raw materials for preparing the composite carbon material comprise the Mxene material and a metal organic framework material. The Mxene material is an inorganic compound with a two-dimensional structure, the metal organic framework material is an organic-inorganic hybrid material which is formed by self-assembling an organic ligand and metal ions or clusters through coordination bonds and has intramolecular pores, and the composite carbon material prepared from the Mxene material and the metal organic framework material has the two-dimensional/three-dimensional framework structures of the Mxene material and the metal organic framework material, contains metal oxide and has larger specific surface area and better lithium affinity.
In some embodiments, the mass ratio of the Mxene material to the metal organic framework material is (0.1-0.5): 1; optionally, the mass ratio of the Mxene material to the metal organic framework material is (0.2-0.4): 1. The mass ratio of the Mxene material to the metal organic framework material is within the range, the composite carbon material has a proper two-dimensional/three-dimensional framework structure, the expansion of a negative pole piece can be effectively inhibited while the lithium precipitation on the surface of a negative pole is improved, and the cycle performance of the secondary battery is better.
In some of these embodiments, the metal center of the metal-organic framework material comprises at least one of Ti, fe, cu, zr, zn, and Cr;
optionally, the metal center is Ti.
The metal element has better lithium affinity, and the corresponding metal oxide contained in the prepared composite carbon material can effectively improve the lithium ion transmission in the negative pole piece and reduce the lithium precipitation on the surface of the negative pole.
In some of these embodiments, the organic ligands of the metal-organic framework material comprise at least one of terephthalic acid and trimesic acid;
optionally, the organic ligand is terephthalic acid.
In some of these embodiments, the metal-organic framework material comprises at least one of MIL-125, MOF-5, MIL-88B, MIL-100, MIL-101, uiO-66, and HKUST-1;
optionally, the metal organic framework material is MIL-125.
In some of these embodiments, the method of making the composite carbon material comprises the steps of:
mixing the MXene material and the metal organic framework material to prepare an intermediate;
and pyrolyzing the intermediate at 250-500 ℃ in a protective atmosphere to prepare the composite carbon material.
In the preparation method of the composite carbon material, MXene material and metal organic framework material are mixed to obtain an intermediate with a proper two-dimensional/three-dimensional framework structure, and the intermediate is carbonized by pyrolyzing organic ligands in the metal organic framework material to form amorphous carbon, so that the obtained composite carbon material still retains the framework structures of the MXene material and the metal organic framework material, and lithium precipitation on the surface of a negative pole piece can be effectively reduced.
In some embodiments, the thickness of the negative electrode protection layer is L1, the total thickness of the negative electrode protection layer and the negative electrode active material layer is L2, and the negative electrode sheet satisfies: L1/L2 is more than or equal to 0.05 and less than or equal to 0.4.
In some embodiments, the thickness L1 of the negative electrode protection layer is 8 μm to 15 μm; can be selected from 10 μm to 14 μm.
The thickness and the proportion of the negative electrode protective layer are in the range, under the condition of ensuring the energy density, lithium is not easy to precipitate on the surface of the negative electrode pole piece, and the cycle performance of the secondary battery is improved.
In a second aspect, the present application further provides a method for preparing the negative electrode plate of the first aspect, including the following steps:
preparing a negative electrode protection layer slurry containing the composite carbon material;
forming the negative electrode protective layer on a surface of the negative electrode active material layer away from the negative electrode current collector using the negative electrode protective layer slurry.
In a third aspect, the present application also provides a secondary battery, including the negative electrode tab of the first aspect.
In a fourth aspect, the present application also provides a battery module including the secondary battery of the third aspect described above.
In a fifth aspect, the present application also provides a battery pack including at least one of the secondary battery of the third aspect and the battery module of the fourth aspect.
In a sixth aspect, the present application further provides an electric device including at least one selected from the group consisting of the secondary battery of the third aspect, the battery module of the fourth aspect, and the battery pack of the fifth aspect.
Drawings
Various additional advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the application. Moreover, like reference numerals are used to refer to like elements throughout. In the drawings:
fig. 1 is a schematic view of a secondary battery according to an embodiment of the present application;
fig. 2 is an exploded view of a secondary battery according to an embodiment of the present application shown in fig. 1;
fig. 3 is a schematic view of a battery module according to an embodiment of the present application;
fig. 4 is a schematic view of a battery pack according to an embodiment of the present application;
fig. 5 is an exploded view of the battery pack of fig. 4 according to an embodiment of the present application;
fig. 6 is a schematic view of an electric device in which a secondary battery according to an embodiment of the present application is used as a power source;
description of reference numerals:
1, a battery pack; 2, putting the box body on the box body; 3, a lower box body; 4 a battery module; 5 a secondary battery; 51 a housing; 52 an electrode assembly; 53 cover plate; 6 electric device.
Detailed Description
Hereinafter, embodiments of the negative electrode sheet, the method for producing the same, the secondary battery, the battery module, the battery pack, and the electric device according to the present application are specifically disclosed in detail with reference to the drawings as appropriate. But a detailed description thereof will be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of actually the same structures may be omitted. This is to avoid unnecessarily obscuring the following description, and to facilitate understanding by those skilled in the art. The drawings and the following description are provided for those skilled in the art to fully understand the present application, and are not intended to limit the subject matter recited in the claims.
As disclosed herein, a "range" is defined in terms of lower and upper limits, with a given range being defined by the selection of one lower limit and one upper limit, which define the boundaries of the particular range. Ranges defined in this manner may or may not include endpoints and may be arbitrarily combined, i.e., any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Further, if the minimum range values of 1 and 2 are listed, and if the maximum range values of 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers. In addition, when a parameter is an integer of 2 or more, it is equivalent to disclose that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, if not specifically stated.
All technical and optional features of the present application may be combined with each other to form new solutions, if not otherwise specified.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, if not specifically stated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, and may also comprise steps (b) and (a) performed sequentially. For example, reference to the process further comprising step (c) means that step (c) may be added to the process in any order, for example, the process may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
The terms "comprises" and "comprising" as used herein mean either open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that other components not listed may also be included or included, or that only listed components may be included or included.
In this application, the term "or" is inclusive, if not otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or not present); a is false (or not present) and B is true (or present); or both a and B are true (or present).
The secondary battery, the battery module, the battery pack, and the electric device according to the present invention will be described below with reference to the drawings as appropriate.
In one embodiment of the present application, a secondary battery is provided.
In general, a secondary battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. In the process of charging and discharging the battery, active ions are embedded and separated back and forth between the positive pole piece and the negative pole piece. The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece. The isolating membrane is arranged between the positive pole piece and the negative pole piece, mainly plays a role in preventing the short circuit of the positive pole and the negative pole, and can enable ions to pass through.
Negative pole piece
The negative pole piece comprises a negative pole current collector, a negative pole active material layer and a negative pole protective layer. The negative active material layer is disposed on at least one surface of the negative current collector. Wherein, the negative electrode protective layer is arranged on the surface of the negative electrode active material layer far away from the negative electrode current collector. The negative electrode protection layer includes a composite carbon material; the composite carbon material comprises MXene material and three-dimensional inorganic carbon material, wherein the three-dimensional inorganic carbon material contains metal oxide.
According to the negative pole piece, the negative pole protective layer containing the specific composite carbon material is arranged, the composite carbon material has a two-dimensional/three-dimensional composite structure and high lithium affinity, lithium precipitation on the surface of the negative pole piece can be reduced, and the secondary battery has good cycle performance.
MXene materials are a class of inorganic compounds with a two-dimensional structure consisting of several atomic layer thick transition metal carbides, nitrides or carbonitrides. The MXene material has the characteristics of excellent conductivity, low lithium ion diffusion barrier, rich lithium-philic functional groups and the like, and has higher strength and flexibility. Compared with the traditional two-dimensional carbon material, the MXene material has better lithium affinity, has the density far higher than that of the traditional carbon material, and can not influence the compaction density of the pole piece when being used for preparing the negative pole piece.
The three-dimensional inorganic carbon material containing the metal oxide has a three-dimensional skeleton structure, contains the metal oxide, can further improve lithium ion transmission of the negative electrode plate, and is more favorable for improving the lithium ion transmission compared with the traditional three-dimensional carbon material.
The composite carbon material comprising the MXene material and the three-dimensional inorganic carbon material is used for preparing the negative electrode protection layer, can effectively improve the lithium precipitation on the surface of the negative electrode, and improves the cycle performance of the secondary battery.
In some of these embodiments, the MXene material comprises Ti 3 C 2 T x 、Ti 4 C 3 Tx、Ti 2 CT x 、V 2 CT x And Nb 2 CT x At least one of, wherein T x Representing a functional group of MXene materials, T x including-OH. Alternatively, T x Further comprising at least one of = O, -F and-Cl. Further, MXene material is Ti 3 C 2 T x 。
In some embodiments, the three-dimensional inorganic carbon material contains a carboxyl group, and the Mxene material is connected to the three-dimensional inorganic carbon material through an ester bond. The Mxene material and the three-dimensional inorganic carbon material are connected through ester bond covalent bonds, a stable two-dimensional/three-dimensional framework structure is formed in the negative electrode protection layer, lithium ion transmission can be improved, lithium precipitation on the surface of a negative electrode plate is avoided, meanwhile, the cyclic expansion of the negative electrode plate can be improved, and the cycle performance of the secondary battery is better.
In some of these embodiments, the composite carbon material has a specific surface area of 26m 2 /g～67m 2 (iv) g. Alternatively, the specific surface area of the composite carbon material is 26.92m 2 /g～66.04m 2 (ii) in terms of/g. The specific surface area of the composite carbon material may be in the range of any of the following numerical compositions: 26m 2 /g、30m 2 /g、35m 2 /g、40m 2 /g、45m 2 /g、50m 2 /g、55m 2 /g、60m 2 /g、65m 2 (iv)/g or 67m 2 (ii) in terms of/g. The specific surface area refers to the total area per unit mass of the material. The specific surface area can be measured by methods well known to those skilled in the art. By way of example, the specific surface area of the composite carbon material can be calculated by a multipoint Brunauer-Emmett-Teller method after a nitrogen isothermal adsorption and desorption curve of the material is measured by a full-automatic gas adsorption analyzer.
In some of these embodiments, the pore size of the composite carbon material is between 5nm and 21nm, optionally, the pore size of the composite carbon material is between 5.2nm and 20.1nm. The pore diameter of the composite carbon material may be in the range of any of the following numerical values: 5nm, 6nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm or 21nm. The pore size of the composite carbon material refers to the average pore size of the composite carbon material, and is a well-known meaning in the art and can be tested by methods known in the art. According to the average pore size evaluation method, GB/T19587-2017 and GB/T21650.2-2008 are referred, a TriStar 3020 type pore size distribution instrument is adopted for testing, adsorption gas is adsorbed on a material to be tested under a series of gradually increased pressures at a constant temperature, and the pore size distribution of the composite carbon material can be represented through a curve diagram of the volume of each level of pore size and the corresponding partial pressure; while the average pore size can be calculated.
The composite carbon material has a high specific surface area and a rich pore diameter structure, is beneficial to improving lithium ion transmission, can fix lithium dendrites and other dead lithium in a negative electrode protective layer, and avoids the problems of pulverization and expansion of a negative electrode plate and the like caused by lithium dendrites and other dead lithium.
In some of these embodiments, the metal oxide comprises TiO 2 、ZnO、Fe 3 O 4 、Cr 2 O 3 、ZrO 2 And CuO; alternatively, the metal oxide is TiO 2 . The metal oxide has better lithium affinity, and can improve the wettability of the negative pole piece to lithium ions, thereby improving the transmission of the lithium ions and reducing the internal resistance of the secondary battery.
In some embodiments, the raw materials for preparing the composite carbon material comprise an Mxene material and a metal organic framework material. The Mxene material is an inorganic compound with a two-dimensional structure, the metal organic framework material is an organic-inorganic hybrid material which is formed by self-assembling an organic ligand and metal ions or clusters through coordination bonds and has intramolecular pores, and the composite carbon material prepared from the Mxene material and the metal organic framework material has the two-dimensional/three-dimensional framework structures of the Mxene material and the metal organic framework material, contains metal oxide and has larger specific surface area and better lithium affinity.
In some embodiments, the mass ratio of the Mxene material to the metal organic framework material is (0.1-0.5): 1; optionally, the mass ratio of the Mxene material to the metal organic framework material is (0.2-0.4): 1. The mass ratio of the Mxene material to the metal organic framework material is within the range, the composite carbon material has a proper two-dimensional/three-dimensional framework structure, the expansion of a negative pole piece can be effectively inhibited while the lithium precipitation on the surface of a negative pole is improved, and the cycle performance of the secondary battery is better.
In some of these embodiments, the metal center of the metal-organic framework material comprises at least one of Ti, fe, cu, zr, zn, and Cr; optionally, the metal center is Ti.
The metal element has better lithium affinity, and the corresponding metal oxide contained in the prepared composite carbon material can effectively improve the lithium ion transmission in the negative pole piece and reduce the lithium precipitation on the surface of the negative pole.
In some of these embodiments, the organic ligands of the metal-organic framework material comprise at least one of terephthalic acid and trimesic acid; alternatively, the organic ligand is terephthalic acid.
In some of these embodiments, the metal organic framework material comprises at least one of MIL-125, MOF-5, MIL-88B, MIL-100, MIL-101, uiO-66, and HKUST-1; optionally, the metal organic framework material is MIL-125.
In some of the embodiments, the method for preparing the composite carbon material includes the following steps S110, S120:
s110: mixing MXene material and metal organic framework material to prepare an intermediate.
S120: and pyrolyzing the intermediate at 250-500 ℃ in a protective atmosphere to prepare the composite carbon material. Alternatively, the temperature of pyrolysis may be in the range consisting of any of the following values: 250 ℃, 300 ℃, 350 ℃,400 ℃, 450 ℃ or 500 ℃. Further, the temperature of pyrolysis is 400 ℃ to 500 ℃. When the pyrolysis temperature is too low, the organic ligand of the metal organic framework material is not enough to be carbonized to form an inorganic carbon material; when the pyrolysis temperature is too high, the three-dimensional inorganic carbon material formed by carbonization contains no carboxyl group.
In the preparation method of the composite carbon material, MXene material and metal organic framework material are mixed to obtain an intermediate with a proper two-dimensional/three-dimensional framework structure, organic ligands in the metal organic framework material are pyrolyzed and carbonized to form amorphous carbon rich in carboxyl, the obtained composite carbon material still retains the framework structures of the MXene material and the metal organic framework material, and lithium deposition on the surface of a negative pole piece can be effectively reduced.
In some embodiments, the thickness of the negative electrode protection layer is L1, the total thickness of the negative electrode protection layer and the negative electrode active material layer is L2, and the negative electrode sheet satisfies: L1/L2 is more than or equal to 0.05 and less than or equal to 0.4. Further, L1/L2 is more than or equal to 0.1 and less than or equal to 0.4. In some of these embodiments, the negative electrode protective layer has a thickness of 8 μm to 15 μm. Alternatively, the thickness of the negative electrode protection layer is 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, or 15 μm. Further, the thickness of the negative electrode protective layer is 10 μm to 14 μm. The thickness of the negative electrode protective layer and the thickness ratio of the negative electrode protective layer to the negative electrode active material layer are within the above range, and under the condition of ensuring energy density, lithium is not easy to precipitate on the surface of the negative electrode pole piece, so that the cycle performance of the secondary battery is improved.
As an example, the thicknesses of the above-described anode protective layer and anode active material layer may be tested according to the following methods: and (3) shearing the cold-pressed negative pole piece into a sample with the size of 6cm to 6cm, and polishing by using an IB-19500CP ion section polisher to obtain a polished sample with a cutting surface. The samples were then tested using ZEISS sigma 300 equipment according to standard JY/T010-1996. And randomly selecting 10 different positions in the test sample for testing, and averaging to obtain the thicknesses of the negative electrode protective layer and the negative electrode active material layer and the total thickness of the negative electrode protective layer and the negative electrode active material layer.
In some embodiments, the mass percentage of the composite carbon material in the negative electrode protective layer is 90% to 98%. Optionally, in the negative electrode protection layer, the mass percentage of the composite carbon material may be in a range of any value composition as follows: 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, or 98%. Further, in the negative electrode protection layer, the mass percentage content of the composite carbon material is 96-97.5%. The mass content of the composite carbon material in the negative electrode protective layer is in the range, the surface lithium precipitation of the negative electrode pole piece can be effectively reduced, and the secondary battery has better cycle performance.
In some of these embodiments, the negative electrode protective layer may optionally further include a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some of these embodiments, the negative electrode protective layer further optionally includes a conductive agent. The conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some of these embodiments, the negative electrode protection layer may also optionally include other adjuvants, such as thickeners (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
As an example, the negative electrode current collector has two surfaces opposite in its own thickness direction, and the negative electrode active material layer is disposed on either or both of the two surfaces opposite to the negative electrode current collector.
In some of the embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil can be used. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base material. The composite current collector can be formed by forming a metal material such as copper, a copper alloy, nickel, a nickel alloy, titanium, a titanium alloy, silver, or a silver alloy on a polymer base material. The polymer material substrate includes substrates such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), and the like.
In some of the embodiments, the negative active material may be a negative active material for a battery known in the art. As an example, the negative active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate and the like. The silicon-based material may be selected from at least one of elemental silicon, silicon oxy-compounds, silicon-carbon compounds, silicon-nitrogen compounds, and silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin oxide compounds, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery negative active material may also be used. These negative electrode active materials may be used alone or in combination of two or more.
In some of these embodiments, the negative active material layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some of these embodiments, the negative active material layer further optionally includes a conductive agent. The conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some of these embodiments, the negative electrode active material layer may also optionally include other adjuvants, such as thickeners (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some of these embodiments, the negative electrode sheet can be prepared by: dispersing the components for preparing the negative electrode plate, such as the composite carbon material, the negative electrode active material, the conductive agent, the binder and any other components, in a solvent (such as deionized water) to form negative electrode active material layer slurry and negative electrode protective layer slurry; coating the negative active material layer slurry on a negative current collector to form a negative active material layer; coating the negative electrode protection layer slurry on the surface of the negative electrode active material layer to form a negative electrode protection layer; and drying, cold pressing and the like to obtain the negative pole piece.
Positive pole piece
The positive pole piece comprises a positive pole current collector and a positive pole active material layer arranged on at least one surface of the positive pole current collector, wherein the positive pole active material layer comprises a positive pole active material.
As an example, the positive electrode current collector has two surfaces opposite in its own thickness direction, and the positive electrode active material layer is disposed on either or both of the two surfaces opposite to the positive electrode current collector.
In some of the embodiments, the positive electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector may be formed by forming a metal material such as aluminum, an aluminum alloy, nickel, a nickel alloy, titanium, a titanium alloy, silver, or a silver alloy on a polymer material base material. The polymer material substrate includes substrates such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), and the like.
In some embodiments, the positive active material may be a positive active material for a battery, which is well known in the art. As an example, the positive electrode active material may include at least one of the following materials: olivine structured lithium-containing phosphorusAcid salts, lithium transition metal oxides and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as a positive electrode active material of a battery may be used. These positive electrode active materials may be used alone or in combination of two or more. Among them, examples of the lithium transition metal oxide may include, but are not limited to, lithium cobalt oxide (e.g., liCoO) 2 ) Lithium nickel oxide (e.g., liNiO) 2 ) Lithium manganese oxide (e.g., liMnO) 2 、LiMn 2 O 4 ) Lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (e.g., liNi) 1/3 Co 1/3 Mn 1/3 O 2 (may also be abbreviated as NCM) 333 )、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (may also be abbreviated as NCM) 523 )、LiNi 0.5 Co 0.25 Mn 0.25 O 2 (may also be abbreviated as NCM) 211 )、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (may also be abbreviated as NCM) 622 )、LiNi 0.8 Co 0.1 Mn 0.1 O 2 (may also be abbreviated as NCM) 811 ) Lithium nickel cobalt aluminum oxides (e.g., liNi) 0.85 Co 0.15 Al 0.05 O 2 ) And modified compounds thereof, and the like. Examples of olivine structured lithium-containing phosphates may include, but are not limited to, lithium iron phosphate (e.g., liFePO) 4 (also referred to as LFP for short)), a composite material of lithium iron phosphate and carbon, and lithium manganese phosphate (e.g., liMnPO) 4 ) At least one of a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
In some of these embodiments, the positive active material layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluoroacrylate resin.
In some of these embodiments, the positive active material layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some of these embodiments, the positive electrode sheet can be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and coating the positive electrode slurry on a positive electrode current collector, and drying, cold pressing and the like to obtain the positive electrode piece.
Electrolyte
The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece. The kind of the electrolyte is not particularly limited and may be selected as desired. For example, the electrolyte may be liquid, gel, or all solid.
In some of these embodiments, the electrolyte is an electrolyte. The electrolyte includes an electrolyte salt and a solvent.
In some of these embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonylimide, lithium bis-trifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium dioxalate phosphate, and lithium tetrafluorooxalate phosphate.
In some of these embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone, and diethyl sulfone.
In some of these embodiments, the electrolyte further optionally includes an additive. For example, the additives may include a negative electrode film-forming additive, a positive electrode film-forming additive, and may further include additives capable of improving certain properties of the battery, such as an additive for improving overcharge properties of the battery, an additive for improving high-temperature or low-temperature properties of the battery, and the like.
Isolation film
In some of the embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known separator having a porous structure and good chemical and mechanical stability may be used.
In some embodiments, the material of the isolation film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some of the embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some of these embodiments, the secondary battery may include an outer package. The exterior package may be used to enclose the electrode assembly and electrolyte.
In some of these embodiments, the outer package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The outer package of the secondary battery may also be a pouch, such as a pouch-type pouch. The material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
The shape of the secondary battery is not particularly limited, and may be a cylindrical shape, a square shape, or any other arbitrary shape. For example, fig. 1 is a secondary battery 5 of a square structure as an example.
In some of these embodiments, referring to fig. 2, the overwrap may include a housing 51 and a cover plate 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose to form an accommodating cavity. The housing 51 has an opening communicating with the accommodating chamber, and a cover plate 53 can be provided to cover the opening to close the accommodating chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is enclosed within the receiving cavity. The electrolyte is impregnated into the electrode assembly 52. The number of electrode assemblies 52 contained in the secondary battery 5 may be one or more, and those skilled in the art can select them according to the actual needs.
In some embodiments, the secondary batteries may be assembled into a battery module, and the number of the secondary batteries contained in the battery module may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module.
Fig. 3 is a battery module 4 as an example. Referring to fig. 3, in the battery module 4, a plurality of secondary batteries 5 may be arranged in series along the longitudinal direction of the battery module 4. Of course, the arrangement may be in any other manner. The plurality of secondary batteries 5 may be further fixed by a fastener.
Alternatively, the battery module 4 may further include a case having an accommodation space in which the plurality of secondary batteries 5 are accommodated.
In some embodiments, the battery modules may be assembled into a battery pack, and the number of the battery modules contained in the battery pack may be one or more, and the specific number may be selected by one skilled in the art according to the application and the capacity of the battery pack.
Fig. 4 and 5 are a battery pack 1 as an example. Referring to fig. 4 and 5, a battery pack 1 may include a battery case and a plurality of battery modules 4 disposed in the battery case. The battery box comprises an upper box body 2 and a lower box body 3, wherein the upper box body 2 can be covered on the lower box body 3, and an enclosed space for accommodating the battery module 4 is formed. A plurality of battery modules 4 may be arranged in any manner in the battery box.
In addition, this application still provides an electric installation, and electric installation includes at least one in secondary battery, battery module or the battery package that this application provided. The secondary battery, the battery module, or the battery pack may be used as a power source of the electric device, and may also be used as an energy storage unit of the electric device. The electric device may include, but is not limited to, a mobile device, an electric vehicle, an electric train, a ship and a satellite, an energy storage system, and the like. The mobile device may be, for example, a mobile phone, a notebook computer, or the like; the electric vehicle may be, for example, a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, or the like, but is not limited thereto.
As the electricity-using device, a secondary battery, a battery module, or a battery pack may be selected according to its use requirement.
Fig. 6 is an electric device 6 as an example. The electric device 6 is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. In order to meet the demand of the electric device for high power and high energy density of the secondary battery, a battery pack or a battery module may be used.
As another example, the device may be a cell phone, a tablet, a laptop, etc. The device is generally required to be thin and light, and a secondary battery may be used as a power source.
Examples
Hereinafter, examples of the present application will be described. The following embodiments are described as illustrative only and are not to be construed as limiting the present application. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. The following examples are directed primarily to composite carbon materials Ti 3 C 2 T x /TiO 2 @ C, it is to be understood that in other specific embodiments, the composite carbon material in the negative electrode tab is not limited to Ti 3 C 2 T x /TiO 2 @C。
Example 1:
(1) Preparing a composite carbon material:
(1.1)Ti 3 C 2 T x preparing materials: 0.8g of LiF was added to 10mL of 9M aqueous HCl solution, and then stirred for 10min. Subsequently, 0.5g of TiAl C was slowly added to the above etching solution at room temperature, and kept stirring for 24h. Repeatedly using deionized waterThe acidic mixture was washed and centrifuged until pH ≈ 6. A stable dark green supernatant was observed after 1h centrifugation at 3500 rpm. Finally, the resulting suspension was freeze-dried for 2 days to obtain Ti 3 C 2 T x A nanosheet.
(1.2) MIL-125 preparation: 3g of 1, 4-phthalic acid are dissolved in 54mL of N, N' -dimethylformamide, and 6g of tetrabutyltitanate and 6mL of methanol are added at room temperature with stirring until a clear solution is obtained. The solution was then placed in a 100mL Teflon lined autoclave at 150 ℃ for 24 hours. The resulting white solid was recovered by filtration at room temperature and washed several times with acetone to remove the solvent molecules from the pores. Finally dried overnight in a vacuum oven at 60 ℃.
(1.3)Ti 3 C 2 T x /TiO 2 @ C preparation: mixing MIL-125 to 50mL of Ti 3 C 2 T x In an aqueous solution (2 mg/mL), ti was added 3 C 2 T x The mass ratio of the mixed solution to MIL-125 is 0.3. Then sonicated for 1h to obtain a homogeneous solution. Freeze-drying the collected solution for 2 days to obtain Ti 3 C 2 T x the/MIL-125 composite material. Then Ti is added under Ar atmosphere 3 C 2 T x Pyrolyzing the/MIL-125 composite material at 500 ℃ (heating rate of 5 ℃/min) (carrying out pyrolysis on MIL-125 to obtain TiO 2 A @ C hybrid and rich in carboxyl groups, with Ti 3 C 2 T x Via ester linkage) to obtain Ti 3 C 2 T x /TiO 2 @ C hybrid. Ti prepared in this example 3 C 2 T x /TiO 2 The specific surface area of the material is 49.55m 2 G, pore diameter of 14.1nm.
(2) Preparing a negative pole piece: dissolving active substance artificial graphite, silicon oxide, conductive agent carbon black, binder Styrene Butadiene Rubber (SBR), and thickener carboxymethylcellulose sodium (CMC) in solvent deionized water according to a mass ratio of 72.3. Mixing Ti 3 C 2 T x /TiO 2 @ C, conductive agent carbon black, binder Styrene Butadiene Rubber (SBR)And the thickener sodium carboxymethylcellulose (CMC) is prepared from the following components in a mass ratio of 96.2:0.8:0.8:1.2 dissolving in solvent deionized water, and preparing into protective layer slurry after uniformly mixing; and coating the protective layer slurry on the negative pole piece, and drying, cold-pressing and slitting to obtain the negative pole piece with the protective layer. The thickness L1 of the negative electrode protective layer was 10 μm, the total thickness L2 of the negative electrode protective layer and the negative electrode active material layer was 100 μm, and L1/L2 was 0.1.
(3) Preparing a positive pole piece: the positive electrode active material NCM811, the conductive agent carbon black, the binder polyvinylidene fluoride (PVDF), and the N-methylpyrrolidone (NMP) were uniformly stirred and mixed in a mass ratio of 95.84. And uniformly coating the positive electrode slurry on a positive electrode current collector, and then drying, cold pressing and cutting to obtain the positive electrode piece.
(4) Preparing an electrolyte: in an argon atmosphere glove box, an organic solvent of Ethylene Carbonate (EC)/Ethyl Methyl Carbonate (EMC)/diethyl carbonate (DEC) was uniformly mixed in a volume ratio of 36 6 And dissolving the lithium salt in the organic solvent, and uniformly stirring to obtain the electrolyte.
(5) Preparing a secondary battery: the method comprises the following steps of taking a polypropylene film as an isolating film, stacking an anode plate, the isolating film and a cathode plate in sequence, enabling the isolating film to be positioned between the anode plate and the cathode plate to play an isolating role, then winding to obtain a naked battery cell, welding a tab for the naked battery cell, packaging the naked battery cell into an aluminum shell, baking at 80 ℃ to remove water, immediately injecting electrolyte and sealing to obtain the uncharged battery. And the uncharged battery sequentially undergoes the working procedures of standing, hot and cold pressing, formation, shaping, capacity testing and the like to obtain a secondary battery product.
Example 2:
example 2 differs from example 1 in that (1.3) Ti 3 C 2 T x /TiO 2 @ C preparation of Ti 3 C 2 T x And the mass ratio of the Ti to the MIL-125 is 0.1 3 C 2 T x /TiO 2 The specific surface area of the material @ C is 66.04m 2 (ii)/g, pore diameter is 5.2nm.
Example 3:
examples3 differs from example 1 in that (1.3) Ti 3 C 2 T x /TiO 2 @ C preparation of Ti 3 C 2 T x And the mass ratio of the Ti to the MIL-125 is 0.2 3 C 2 T x /TiO 2 @ C material has a specific surface area of 55.69m 2 (ii)/g, pore diameter 9.8nm.
Example 4:
example 4 differs from example 1 in that (1.3) Ti 3 C 2 T x /TiO 2 @ C preparation of Ti 3 C 2 T x And the mass ratio of the Ti to the MIL-125 is 0.4 3 C 2 T x /TiO 2 The specific surface area of the material is 37.23m 2 G, pore diameter of 18.4nm.
Example 5:
example 5 differs from example 1 in that (1.3) Ti 3 C 2 T x /TiO 2 @ C preparation of Ti 3 C 2 T x And the mass ratio of the Ti to the MIL-125 is 0.5 3 C 2 T x /TiO 2 The specific surface area of the @ C material is 26.92m 2 G, pore diameter of 20.1nm.
Examples 6 to 9:
examples 6 to 9 are different from example 1 in the thickness L1 and the ratio L1/L2 of the negative electrode protective layer. In example 6, the thickness L1 of the negative electrode protection layer was 5 μm, and L1/L2 was 0.05. In example 7, the thickness L1 of the negative electrode protection layer was 20 μm, and L1/L2 was 0.2. In example 8, the thickness L1 of the negative electrode protection layer was 30 μm, and L1/L2 was 0.3. In example 9, the thickness L1 of the negative electrode protection layer was 40 μm, and L1/L2 was 0.4.
Comparative example 1:
comparative example 1 is different from example 1 in that the negative electrode tab of comparative example 1 does not contain a negative electrode protection layer. The thickness of the negative electrode active material layer was 90 μm.
Comparative example 2:
comparative example 2 is different from example 1 in that in (2) negative electrode sheet preparation of comparative example 2, ti 3 C 2 T x /TiO 2 Substitution of the material @ C for Ti prepared in (1.1) 3 C 2 T x ，Ti 3 C 2 T x The specific surface area of the material is 16.52m 2 G, pore diameter of 21.5nm.
Comparative example 3:
comparative example 3 is different from example 1 in that in (2) negative electrode sheet preparation of comparative example 3, ti 3 C 2 T x /TiO 2 Substitution of the material @ C with TiO 2 @ C material, tiO 2 The @ C material was prepared as follows: subjecting MIL-125 to 500 deg.C (heating rate 5 deg.C/min) pyrolysis in Ar atmosphere to obtain TiO 2 @C，TiO 2 The specific surface area of the material is 103.67m 2 (ii)/g, pore diameter is 4.1nm.
Test part:
testing the thickness of the negative pole piece: and cutting the cold-pressed negative pole piece into a sample with the size of 6cm to 6cm, and polishing by using an IB-19500CP ion section polisher to obtain a polished sample with a cutting surface. The samples were then tested with ZEISS sigma 300 equipment according to standard JY/T010-1996. And randomly selecting 10 different positions in the test sample for testing, and averaging to obtain the total thickness of the negative electrode protection layer and the negative electrode film layer and the ratio of the thickness of the negative electrode protection layer to the total thickness of the negative electrode film layer.
And (3) testing the rebound rate of the negative pole piece: the thickness h0 of the freshly prepared negative electrode sheet (not subjected to the cycling test) was measured with a ten-thousandth ruler. Then, a secondary battery is prepared by using the pole piece.
Charging a newly-prepared secondary battery to 4.25V at a constant current of 1/3C, charging the battery to 0.1C at a constant voltage of 4.25V, discharging the battery to 2.5V at 0.33C, completing a cycle, repeating the cycle of 400cls, charging the battery to 4.25V when the battery is fully charged (the voltage window is 2.5V-4.25V), disassembling the battery, taking out a fully-charged negative pole piece, measuring the thickness (h 1) of the negative pole piece at the moment by a ten-thousandth ruler, and determining the rebound rate of the pole piece = (h 1/h 0-1) multiplied by 100 percent
And (3) energy density testing: at 25 ℃, the material was charged to 4.25v at 0.33C standard, charged to 0.05C at a constant voltage of 4.25v, left to stand for 10min, and then discharged to 2.5V at 0.33C, and the discharge capacity was recorded, followed by calculation of the energy density at the time of discharge. Energy density (Wh/kg) = discharge capacity (Wh)/secondary battery mass (kg).
And (3) testing the cycle performance: the secondary battery was charged at a constant current of 1/3C to 4.25V at 25 ℃, further charged at a constant voltage of 4.25V to a current of 0.05C, left for 5min, and then discharged at 1/3C to 2.5V, and the measured capacity was designated as initial capacity C0. When the above steps are repeated for the same cell and the discharge capacity Cn of the cell after the n-th cycle is recorded at the same time, the cell capacity retention ratio Pn = Cn/C0 × 100% after the n-th cycle (i.e., n cycles (cls)).
Cyclic DCR growth test: charging the newly prepared secondary battery to 4.25V at constant current of 1/3C at 25 deg.C, charging to 0.05C at constant voltage of 4.25V, discharging to 2.5V at 1/3C, extracting the change of voltage before and after 30s at the beginning of discharge to be delta U, changing the change of current before and after to be delta I, obtaining the discharge DCR value = delta U/delta I, measuring the DCR value D0 of the charging process, and standing for 5 min. Repeating the above steps for the same cell, and simultaneously recording the DCR value D1 of the cell after n cycles, the DCR increase rate Dn = Dn/D0 × 100% after n cycles (i.e., n cycles (cls)).
Electrochemical performance test data of the secondary batteries of examples 1 to 9 and comparative examples 1 to 3 are recorded in table 1.
TABLE 1 compositions and electrochemical properties of secondary batteries of examples 1 to 9 and comparative examples 1 to 3
As can be seen from the data in table 1, the energy density of the secondary batteries of examples 1 to 9 is 225Wh/kg to 231Wh/kg, the capacity retention rate after 400cls cycle is 98.7% to 99.4%, the negative electrode sheet rebound rate is 26% to 38%, and the DCR growth rate is 105% to 114%; the secondary batteries of embodiments 1 to 9 have high retention rate of 400cls cycle capacity, small rebound rate of a negative electrode plate, small growth rate of DCR of the secondary battery and good cycle performance while ensuring high energy density.
The secondary battery of comparative example 1, in which the negative electrode tab was not provided with the negative electrode protection layer, had an energy density of 232Wh/kg, a capacity retention rate after 400cls cycle of 96.5%, a negative electrode tab rebound rate of 41%, and a DCR growth rate of 127%. The secondary battery of comparative example 1 is not provided with a negative electrode protection layer, the energy density of the secondary battery is slightly higher than that of the secondary batteries of examples 1 to 9, but the cycle capacity retention rate of comparative example 1 is lower than that of examples 1 to 9, the rebound rate of the negative electrode sheet and the DCR growth rate of the secondary battery of comparative example 1 are higher than those of examples 1 to 9, and it can be seen that the secondary battery of comparative example 1 has obvious cycle deterioration and obviously inferior cycle performance to those of the secondary batteries of examples 1 to 9.
In the secondary batteries of comparative examples 2 and 3, the components of the negative electrode protective layer were Ti 3 C 2 T x Material and TiO 2 @ C material. The secondary batteries of comparative examples 2 to 3 were slightly superior in cycle performance to the secondary battery of comparative example 1, but inferior to the secondary batteries of examples 1 to 9.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present application, so as to understand the technical solutions of the present application in detail and in detail, but not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. It should be understood that the technical solutions provided by the present application and obtained by logical analysis, reasoning or limited experiments by those skilled in the art are all within the scope of the appended claims. Therefore, the protection scope of the present patent application shall be subject to the content of the appended claims, and the description and the drawings shall be used for explaining the content of the claims.
Claims (20)
1. A negative electrode sheet, comprising:
a negative current collector;
a negative electrode active material layer disposed on at least one surface of the negative electrode current collector; and
the negative electrode protective layer is arranged on the surface of the negative electrode active material layer, which is far away from the negative electrode current collector; the negative electrode protection layer includes a composite carbon material; the composite carbon material comprises an MXene material and a three-dimensional inorganic carbon material, wherein the three-dimensional inorganic carbon material contains a metal oxide.
2. The negative electrode tab of claim 1, wherein the MXene material comprises Ti 3 C 2 T x 、Ti 4 C 3 Tx、Ti 2 CT x 、V 2 CT x And Nb 2 CT x At least one of (1), wherein T x Functional group representing MXene Material, T x comprises-OH; alternatively, T x Further comprising at least one of = O, -F, and-Cl.
3. The negative electrode sheet according to claim 2, wherein the three-dimensional inorganic carbon material contains a carboxyl group, and the Mxene material is connected to the three-dimensional inorganic carbon material by an ester bond.
4. The negative electrode tab according to claim 1, wherein the specific surface area of the composite carbon material is 26m 2 /g～67m 2 G, optionally 26.92m 2 /g～66.04m 2 /g。
5. The negative electrode sheet according to claim 1, wherein the pore diameter of the composite carbon material is 5nm to 21nm, optionally 5.2nm to 20.1nm.
6. The negative electrode sheet as claimed in claim 1, wherein the negative electrode sheet is a lithium secondary batteryThe metal oxide comprises TiO 2 、ZnO、Fe 3 O 4 、Cr 2 O 3 、ZrO 2 And CuO;
optionally, the metal oxide is TiO 2 。
7. The negative electrode sheet according to claim 1, wherein the composite carbon material is contained in the negative electrode protective layer in an amount of 90 to 98% by mass;
optionally, in the negative electrode protection layer, the mass percentage of the composite carbon material is 96% to 97.5%.
8. The negative electrode sheet according to any one of claims 1 to 7, wherein the raw materials for preparing the composite carbon material comprise the Mxene material and a metal organic framework material.
9. The negative pole piece of claim 8, wherein the mass ratio of the Mxene material to the metal organic frame material is (0.1-0.5): 1;
optionally, the mass ratio of the Mxene material to the metal organic framework material is (0.2-0.4): 1.
10. The negative electrode tab of claim 8, wherein the metal center of the metal-organic framework material comprises at least one of Ti, fe, cu, zr, zn, and Cr;
optionally, the metal center is Ti.
11. The negative electrode sheet of claim 8, wherein the organic ligand of the metal-organic framework material comprises at least one of terephthalic acid and trimesic acid;
optionally, the organic ligand is terephthalic acid.
12. The negative electrode sheet of claim 8, wherein the metal organic framework material comprises at least one of MIL-125, MOF-5, MIL-88B, MIL-100, MIL-101, uiO-66, and HKUST-1;
optionally, the metal organic framework material is MIL-125.
13. The negative electrode sheet according to claim 8, wherein the method for preparing the composite carbon material comprises the following steps:
mixing the MXene material and the metal organic framework material to prepare an intermediate;
and pyrolyzing the intermediate at 250-500 ℃ in a protective atmosphere to prepare the composite carbon material.
14. The negative electrode plate as claimed in any one of claims 1 to 7 and 9 to 13, wherein the thickness of the negative electrode protection layer is L1, the total thickness of the negative electrode protection layer and the negative electrode active material layer is L2, and the negative electrode plate satisfies the following conditions: L1/L2 is more than or equal to 0.05 and less than or equal to 0.4.
15. The negative electrode tab according to any one of claims 1 to 7 and 9 to 13, wherein the thickness L1 of the negative electrode protective layer is 8 to 15 μm; can be selected from 10 μm to 14 μm.
16. The method for preparing the negative electrode plate of any one of claims 1 to 15, characterized by comprising the steps of:
preparing a negative electrode protection layer slurry containing the composite carbon material;
and forming the negative electrode protection layer on the surface of the negative electrode active material layer away from the negative electrode current collector by using the negative electrode protection layer slurry.
17. A secondary battery comprising the negative electrode sheet according to any one of claims 1 to 15.
18. A battery module characterized by comprising the secondary battery according to claim 17.
19. A battery pack comprising at least one of the secondary battery according to claim 17 and the battery module according to claim 18.
20. An electric device comprising at least one selected from the group consisting of the secondary battery according to claim 17, the battery module according to claim 18, and the battery pack according to claim 19.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210846140.5A CN115832242A (en) | 2022-07-19 | 2022-07-19 | Negative pole piece and preparation method thereof, secondary battery, battery module, battery pack and electric device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210846140.5A CN115832242A (en) | 2022-07-19 | 2022-07-19 | Negative pole piece and preparation method thereof, secondary battery, battery module, battery pack and electric device |
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