CN115353097B - Graphene nanotube, positive electrode slurry, positive electrode sheet, battery cell and electronic device - Google Patents
Graphene nanotube, positive electrode slurry, positive electrode sheet, battery cell and electronic device Download PDFInfo
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- CN115353097B CN115353097B CN202210988163.XA CN202210988163A CN115353097B CN 115353097 B CN115353097 B CN 115353097B CN 202210988163 A CN202210988163 A CN 202210988163A CN 115353097 B CN115353097 B CN 115353097B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 61
- 239000002071 nanotube Substances 0.000 title claims abstract description 60
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 23
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 17
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 17
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- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000007774 positive electrode material Substances 0.000 claims description 38
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000011534 incubation Methods 0.000 claims description 4
- 229920002313 fluoropolymer Polymers 0.000 claims description 3
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- 150000001875 compounds Chemical class 0.000 claims description 2
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- 239000002245 particle Substances 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 36
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- 238000012360 testing method Methods 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
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- 238000000034 method Methods 0.000 description 6
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
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- 238000005520 cutting process Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
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- 101150058243 Lipf gene Proteins 0.000 description 1
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- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
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- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- 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
Abstract
The application relates to a graphene nanotube, positive electrode slurry, a positive electrode plate, an electric core and electronic equipment, and belongs to the technical field of batteries. The preparation method of the graphene nanotube comprises the following steps: mixing the multiwall carbon nanotubes, potassium nitrate and concentrated sulfuric acid, and stirring to form a mixed solution; mixing potassium permanganate with the mixed solution, stirring, heating in a water bath, and preserving heat for a period of time to obtain a reaction solution after the reaction is completed; and cooling the reaction liquid to room temperature, uniformly mixing the reaction liquid with a hydrogen peroxide solution and an ice-water mixture, and washing and centrifuging the reaction liquid to obtain the graphene nanotube. The graphene nanotube provided by the application has excellent conductivity and larger surface area, and the unique tubular structure of the graphene nanotube can enable LiFePO to be formed 4 The particles are connected to improve the conductivity between them, thereby improving the LiFePO-based 4 The multiplying power performance of the battery core, the cycle performance under the high multiplying power condition and the low temperature performance.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a graphene nanotube, positive electrode slurry, a positive electrode plate, an electric core and electronic equipment.
Background
Lithium ion batteries are considered to be a promising rechargeable energy storage system capable of replacing fossil fuels due to their high energy density and long cycle life. LiFePO 4 The polyanion type positive electrode material with the olivine structure has the characteristics of high theoretical capacity, environmental friendliness, good safety, long cycle life and low cost, and can be applied to energy storage or power battery projects. LiFePO 4 The positive electrode material limits its charge/discharge rate due to low intrinsic conductivity. To solve this problem, liFePO is generally prepared by coating a highly conductive material, nanostructure formation, element doping, etc 4 The positive electrode material is modified or various carbon materials (carbon black, ethylene black, super P, carbon nano tube, etc.) are used as conductive additives to improve LiFePO during the positive electrode manufacturing process 4 Conductivity between particles to improve LiFePO-based 4 The rate capability and cycle performance of the battery of the positive electrode material. However, conventional LiFePO 4 The conductivity of the particles remains to be improved.
Disclosure of Invention
The purpose of the application is to provide a graphene nanotube, a positive electrode slurry, a positive electrode plate, a battery cell and electronic equipment, wherein the graphene nanotube has excellent conductivity and large surface area, and the unique tubular structure of the graphene nanotube can enable LiFePO 4 The particles are connected to improve the conductivity between them, thereby improving the LiFePO-based 4 The multiplying power performance of the battery core and the cycle performance under the high multiplying power condition.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a graphene nanotube, the preparation method of the graphene nanotube comprising the steps of:
mixing the multiwall carbon nanotubes, potassium nitrate and concentrated sulfuric acid, and stirring to form a mixed solution;
mixing potassium permanganate with the mixed solution, stirring, heating in a water bath, and preserving heat for a period of time to obtain a reaction solution after the reaction is completed;
and cooling the reaction liquid to room temperature, uniformly mixing the reaction liquid with a hydrogen peroxide solution and an ice-water mixture, and washing and centrifuging the reaction liquid to obtain the graphene nanotube.
In some embodiments, the mass ratio of the multiwall carbon nanotubes, the potassium nitrate, the potassium permanganate is (1-1.2): 5:10.
in some embodiments, the water bath temperature is 70 to 100 ℃ and the incubation time is 2 to 10 hours.
In some embodiments, the volume ratio of hydrogen peroxide solution to ice water mixture is 1:69, wherein the mass fraction of the hydrogen peroxide solution is 35%.
The application also provides positive electrode slurry, which comprises a positive electrode active material, a binder, a solvent and the graphene nanotube;
optionally, the positive electrode active material comprises LiFePO 4 。
In some embodiments, the binder comprises a fluoropolymer and the solvent comprises an amide-like compound.
In some embodiments, the mass ratio of the positive electrode active material, the binder, and the graphene nanotubes is (80 to 90): 5: (5-15).
The application also provides a positive plate, which comprises a current collector and a positive active material layer positioned on at least one surface of the current collector, wherein the positive active material layer comprises the positive slurry.
Further, the application also provides a battery cell, which comprises the positive plate;
optionally, the battery cell includes any one of a soft package battery cell, a square aluminum shell battery cell and a cylindrical battery cell.
In addition, the application also provides electronic equipment, which comprises a shell and the battery cell, wherein the battery cell is positioned inside the shell.
Compared with the prior art, the graphene nanotube has the following advantages:
(1) The graphene nanotube has a tubular structure and a large specific surface area, provides an effective channel for ion diffusion, and adds a small amount of graphene nanotube into LiFePO 4 In the positive electrode material, a three-dimensional conductive network can be formed to reduce LiFePO 4 The internal resistance of the positive electrode material improves the conductivity thereof.
(2) The graphene nanotube can be directly added into LiFePO as a conductive agent 4 In the anode material, liFePO in the prior art is avoided 4 The complex process of compounding the graphene and other conductive materials is simple to operate.
(3) The graphene nanotubes are dispersed in LiFePO as a conductive agent 4 The particles enable the prepared positive plate to have excellent multiplying power performance, high multiplying power cycle performance and low temperature performance, and the comprehensive electrochemical performance is outstanding.
Drawings
FIG. 1 is a schematic illustration of a positive electrode material LiFePO used in the present application 4 And SEM pictures of the positive electrode sheets prepared in examples 1 to 3; a is LiFePO 4 B is the positive electrode sheet of example 1, c is the positive electrode sheet of example 2, and d is the positive electrode sheet of example 3.
Fig. 2 is a first charge-discharge diagram of half cells assembled in examples 1-3 and comparative example 1 of the present application.
Fig. 3 is a graph showing a cycle performance comparison of the soft pack cells of examples 1 to 3 and comparative example 1 of the present application at normal temperature for 200 weeks at a current of 5C.
Fig. 4 is a graph showing comparison of cycle performance of the soft pack cells of examples 1 to 3 and comparative example 1 at room temperature for 1200 weeks at 30C.
Fig. 5 is a graph comparing the low temperature performance of the soft pack cells of examples 1-3 and comparative example 1 of the present application at-25 to 25 ℃.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
An embodiment of the present application provides a graphene nanotube, which is prepared by the following steps:
mixing the multiwall carbon nanotubes, potassium nitrate and concentrated sulfuric acid, and stirring to form a mixed solution;
mixing potassium permanganate with the mixed solution, stirring, heating in a water bath, and preserving heat for a period of time to obtain a reaction solution after the reaction is completed;
and cooling the reaction liquid to room temperature, uniformly mixing the reaction liquid with a hydrogen peroxide solution and an ice water mixture, and washing and centrifuging the reaction liquid to obtain the graphene nanotube.
The lithium ion battery has the advantages of small self-discharge, high voltage, high capacity, small volume, no memory effect and the like, and is widely applied to the fields of electric automobiles, notebook computers, digital cameras and the like. Lithium ion batteries have become one of the key points of high-tech development as a new generation of green high-energy batteries with excellent performance. The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm and electrolyte, wherein the positive electrode material occupies more than 40% of the total cost of the lithium ion battery, and the performance of the positive electrode material directly influences the performance of the lithium ion battery, so that the positive electrode material occupies an important position in the lithium ion battery.
The positive electrode material of the lithium ion battery needs to have the following basic properties: the lithium ion battery has the advantages of high discharge voltage, capability of inserting more reversible lithium ions to ensure higher capacity, high diffusion and migration speed of lithium ions and electrons, good chemical stability and simple preparation process, and can meet the requirement of rapid charge and discharge.
Commercial lithium ion battery cathode materials include lithium cobaltate, lithium manganate, ternary materials, lithium iron phosphate, and the like. The lithium cobaltate is the most widely used lithium ion battery anode material at present, has stable capacity, high open-circuit voltage and long cycle life, and compared with ternary materials, the lithium cobaltate has lower capacity and power, and has high toxicity due to the high price of cobalt, so that the lithium cobaltate has a tendency of being replaced. The lithium manganate is mainly produced by taking manganese dioxide and lithium carbonate as raw materials, the cost is low, the production method is simple, the production method is nontoxic and harmless, waste water and waste gas are not generated, the lithium manganate has good safety performance when being used as a positive electrode material of the lithium ion battery, however, the theoretical capacity is low, the cycle performance is poor, and the further development of the lithium ion battery is restricted by the miniaturization trend of the battery. The nickel cobalt lithium manganate ternary material has high theoretical capacity and good cycle performance, is relatively high in cost due to lack of cobalt resources, and has potential safety hazards in the use process. The lithium iron phosphate exists in the natural world in the form of lithium iron phosphate ore, and the chemical molecular formula is LiFePO 4 Lithium is positive monovalent, iron is positive divalent, and phosphate is negative trivalent. LiFePO 4 The lithium ion battery is widely available, does not contain noble metals and rare metals, is manufactured by using the lithium ion battery as a positive electrode material, has the advantages of low cost, environmental friendliness, good cycle performance, wide working temperature range and the like, is considered as the positive electrode material with the most development prospect, and becomes a research hot spot of the positive electrode material in recent years. However due to LiFePO 4 Self-crystal structure limitation, electron conductivity and lithiumThe low ion diffusion coefficient limits the charge rate and discharge rate, preventing further commercial use. Thus, liFePO is improved 4 Has profound significance in terms of conductivity.
The application creatively provides a graphene nanotube, and the graphene nanotube obtained by the preparation method provided by the application has excellent conductivity, ultra-fast electron plane transfer characteristic and very small bulk density, and is oriented to LiFePO 4 The conductive effect of the traditional conductive agent with more additive amount can be achieved by adding a small amount of graphene nanotubes into the positive electrode material, and the graphene nanotubes are used as the conductive agent to be applied to LiFePO 4 In the positive electrode material, the unique tubular structure can conduct LiFePO 4 The effect of the particles can improve LiFePO at the same time 4 The adding proportion of the anode material further improves the multiplying power performance, the cycle performance under the high multiplying power condition and the energy density of the lithium ion battery.
Optionally, the multi-walled carbon nanotubes, potassium nitrate and concentrated sulfuric acid are mixed for 1-10 h, and the stirring time can be, for example, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h. It will be appreciated that the stirring time may also be other values in the range 1 to 10 hours.
Alternatively, the potassium permanganate is mixed with the mixed solution for a stirring time of 1 to 10 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours. It will be appreciated that the stirring time may also be other values in the range 1 to 10 hours.
In some embodiments, the mass ratio of the multiwall carbon nanotubes, the potassium nitrate, the potassium permanganate is (1-1.2): 5:10.
alternatively, the mass ratio of the multiwall carbon nanotubes, potassium nitrate, potassium permanganate may be 1:5:10, or 1.1:5:10, can also be 1.2:5:10. it is understood that the mass ratio of the multi-wall carbon nano tube, the potassium nitrate and the potassium permanganate is (1-1.2): 5: other ratio values in 10.
In some embodiments, the water bath temperature is 70-100 ℃ and the holding time is 2-10 hours.
Alternatively, the water bath temperature may be 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, and the incubation time may be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h. It will be appreciated that the bath temperature may be other values in the range 70 to 100℃and the incubation time may be other values in the range 2 to 10 hours.
In some embodiments, the volume ratio in the hydrogen peroxide and ice water mixture is 1:69, wherein the mass fraction of the hydrogen peroxide solution is 35%.
It should be explained that when the reaction solution is mixed with the hydrogen peroxide solution and the ice-water mixture, the hydrogen peroxide solution plays an oxidation role, and the added ice-water mixture is used for cooling to prevent the volatilization of hydrogen peroxide from affecting the oxidation reaction, so that the addition amount of the ice-water mixture can play a cooling role without strictly controlling the addition amount of the ice-water mixture and the addition ratio of ice and water.
The application also provides positive electrode slurry, which comprises a positive electrode active material, a binder, a solvent and the graphene nanotube;
alternatively, the positive electrode active material includes LiFePO 4 。
It should be noted that the positive electrode active material may be not only LiFePO 4 Carbon coated LiFePO is also possible 4 Or doped with LiFePO from other elements 4 Provided that the positive electrode active material includes LiFePO 4 Then all are in LiFePO of the present application 4 Within a defined range. The anode slurry is coated on foil materials such as aluminum foil and the like, and the solvent is volatilized after drying treatment, so that the quality of an anode active material, a binder and graphene nanotubes in the anode slurry is critical, and the addition amount of the solvent is not required to be strictly controlled.
In some embodiments, the binder comprises a fluoropolymer and the solvent comprises an amide.
In some embodiments, the mass ratio of the positive electrode active material, the binder, and the graphene nanotubes is (80-90): 5: (5-15).
Alternatively, the mass ratio of the positive electrode active material, the binder, and the graphene nanotubes may be 80:5:15, may also be 85:5:10, or 90:5:5. it can be appreciated that the mass ratio of the positive electrode active material, the binder, and the graphene nanotubes may also be (80 to 90): 5: other values in (5-15).
The application also provides a positive plate, which comprises a current collector and a positive active material layer positioned on at least one surface of the current collector, wherein the positive active material layer comprises the positive slurry.
Further, the application also provides a battery cell, which comprises the positive plate;
optionally, the battery cell includes any one of a soft package battery cell, a square aluminum case battery cell and a cylindrical battery cell.
In addition, the application also provides electronic equipment, which comprises a shell and the battery cell, wherein the battery cell is positioned inside the shell.
The present invention will be described in further detail with reference to specific examples and comparative examples. The experimental parameters not specified in the following specific examples are preferentially referred to the guidelines given in the application document, and may also be referred to the experimental manuals in the art or other experimental methods known in the art, or to the experimental conditions recommended by the manufacturer. It is understood that the instruments and materials used in the following examples are more specific and in other embodiments may not be so limited.
Example 1
1. The preparation method of the graphene nanotube comprises the following steps:
adding multiwall carbon nanotubes (MWCNTs) and potassium nitrate into concentrated sulfuric acid, and stirring for 2 hours to form a mixed solution;
adding potassium permanganate into the mixed solution, stirring for 2 hours at room temperature, heating to 70 ℃ in a water bath, preserving heat for 2 hours, and obtaining a reaction solution after the reaction is completed; wherein, the mass ratio of the multiwall carbon nanotube to the potassium nitrate to the potassium permanganate is 1:5:10;
and cooling the reaction liquid to room temperature, adding an ice-water mixture containing a hydrogen peroxide solution, uniformly mixing, repeatedly washing with ethanol, centrifuging to obtain graphene nanotubes, and dispersing the graphene nanotubes in ethanol for later use. Wherein, the volume ratio of the hydrogen peroxide solution to the ice water mixture is 1:69 and the mass fraction of the hydrogen peroxide solution is 35%.
2. Preparation of Positive electrode slurry
Weighing LiFePO with certain mass 4 Uniformly stirring graphene nanotubes and polyvinylidene fluoride (PVDF), and then adding N-methyl pyrrolidone (NMP) for continuous stirring to prepare anode slurry; wherein, liFePO 4 The mass ratio of the graphene nano tube to the polyvinylidene fluoride is 90:5:5.
example 2
Substantially the same as in example 1, except that: when preparing positive electrode slurry, liFePO 4 The mass ratio of the graphene nano tube to the polyvinylidene fluoride is adjusted to be 85:10:5.
example 3
Substantially the same as in example 1, except that: when preparing positive electrode slurry, liFePO 4 The mass ratio of the graphene nanotube to the polyvinylidene fluoride is adjusted to 80:15:5.
example 4
Substantially the same as in example 1, except that: when preparing the graphene nanotube, the mass ratio of the multiwall carbon nanotube to the potassium nitrate to the potassium permanganate is 1.1:5:10.
example 5
Substantially the same as in example 1, except that: when preparing the graphene nanotube, the mass ratio of the multiwall carbon nanotube to the potassium nitrate to the potassium permanganate is 1.2:5:10.
comparative example 1
Substantially the same as in example 1, except that: when preparing the positive electrode slurry, the graphene nanotubes are replaced with Super P.
Comparative example 2
Substantially the same as in example 1, except that: in preparing the positive electrode slurry, graphene nanotubes were replaced with untreated multiwall carbon nanotubes in example 1.
Comparative example 3
Substantially the same as in example 1, except that: when preparing the graphene nanotube, the mass ratio of the multiwall carbon nanotube to the potassium nitrate to the potassium permanganate is 0.9:5:10.
comparative example 4
Substantially the same as in example 1, except that: when preparing the graphene nanotube, the mass ratio of the multiwall carbon nanotube to the potassium nitrate to the potassium permanganate is 1.3:5:10.
test example 1 first charge and discharge test and lithium ion diffusion coefficient test of half cell
1. Preparation of positive electrode sheet
The positive electrode slurries prepared in examples 1 to 5 and comparative examples 1 to 4 were coated on an aluminum foil in an amount of 17mg/cm 2 Baking to obtain a positive plate;
2. assembled half-cell
The assembly method comprises the following steps: firstly rolling a positive plate, then assembling a half battery according to the sequence of a negative electrode shell, a lithium plate, a diaphragm, the rolled positive plate, a gasket, an elastic sheet and the positive electrode shell, wherein the injected electrolyte is 1mo1/LLiPF 6 Ec+dmc (volume ratio 1:1).
3. SEM test
LiFePO is prepared 4 And the positive electrode sheets of examples 1 to 3 were tested under a scanning electron microscope, and the results are shown in fig. 1.
As can be seen from fig. 1, the positive electrode material LiFePO used in the present application 4 The graphene nanotubes added into the positive electrode sheets of examples 1-3 were gradually increased in a long strip shape and a relatively uniform particle size, and the corresponding sheet structure was gradually increased.
4. First charge and discharge test
The assembled half cells were subjected to a first charge and discharge test at a current of 1C and a voltage of 2.0-3.8V, and the test results are shown in table 1 and fig. 2.
Table 1 performance test of half-cells
As can be seen from table 1 and fig. 2, the energy at 3.4V (for Li + Li), the half-cells of examples 1-3 and comparative example 1 each exhibit a voltage plateau corresponding to Fe 3+ /Fe 2+ Is a redox process and a lithium ion extraction/intercalation process; the half cell of comparative example 1 had a discharge gram capacity of 134.8mAh/g,the half cells of comparative example 2 had a discharge gram capacity of 136.2mAh/g, and the half cells of examples 1, 2, 3, 4 and 5 had discharge gram capacities of 141.3mAh/g, 152.1mAh/g, 153.7mAh/g, 142.0mAh/g and 142.2mAh/g, respectively, which were significantly improved as compared to comparative examples 1-2;
in addition, during the charge and discharge of the half cell, the voltage difference of the half cell of comparative example 1 reached 368mV and the voltage difference of the half cell of comparative example 2 reached 279mV, indicating slower lithium ion transport and lower electron conductivity, resulting in greater polarization of the half cells of comparative examples 1-2; the lower voltage differences of the half cells of examples 1-5, 157mV, 119mV, 87mV, 155mV, 159mV, indicate that graphene nanotubes were added as a conductive agent to LiFePO 4 In (3) can reduce LiFePO 4 And as the graphene nanotube content increased, liFePO of examples 1-3 4 Gradually decreasing in polarization ratio. The improved discharge gram capacity and reduced polarization of the half cells of examples 1-5 showed their superiority compared to comparative examples 1-2 due to the graphene nanotubes in LiFePO 4 A developed conductive network is formed among the particles;
as can be seen from comparison of examples 1, examples 4 to 5 and comparative examples 3 to 4, the discharge gram capacity and the voltage difference of the half cell of comparative example 4 are similar or identical to those of examples 4 and 5, which indicates that the mass increase of the multi-walled carbon nanotube does not bring significant change in the discharge gram capacity and the voltage difference of the half cell of comparative example 4 but increases the production cost when the graphene nanotube is prepared.
5. Diffusion coefficient of lithium ion
The half cells prepared in example 2 and comparative example 1 were tested using electrochemical impedance to give LiFePO of example 2 and comparative example 1 4 Lithium ion diffusion coefficient of (2), liFePO of example 4 Is 2.56X10 - 13 cm 2 s -1 LiFePO of comparative example 1 4 Is 1.72X10) -13 cm 2 s -1 Indicating the addition in example 2The graphene nanotube of the lithium ion battery is more beneficial to the diffusion of lithium ions, so that the positive plate formed by the positive electrode slurry is more beneficial to the high-current charge and discharge.
The above-described lithium ion diffusion coefficient test was also performed in examples 1 and 3 to 5, and the result was similar to the lithium ion diffusion coefficient obtained in example 2.
Test example 2 cycle performance and Low temperature Performance test of Soft-packaged cells
1. The preparation method of the soft-package battery cell comprises the following steps:
(1) Preparation of negative electrode slurry
Weighing graphite, carbon black (SP) and sodium carboxymethylcellulose (CMC) with certain mass, uniformly stirring, sequentially adding deionized water and Styrene Butadiene Rubber (SBR), and continuously stirring to obtain negative electrode slurry, wherein the mass ratio of the graphite to the carbon black to the sodium carboxymethylcellulose to the styrene butadiene rubber is 90:5:2.5:2.5;
(2) Preparation of positive electrode sheet and negative electrode sheet
The positive electrode slurry prepared in test example 1 was uniformly coated on an aluminum foil, leaving a blank area as a tab area, the coating amount of the positive electrode slurry was 17mg/cm 2 Baking to obtain a positive plate;
uniformly coating the anode slurry prepared in the step (1) on a copper foil, leaving a blank area as a tab area, wherein the coating amount of the anode slurry is 8mg/cm 2 Baking to obtain a negative plate;
(3) Rolling press
Rolling the positive plate and the negative plate by a roller press, wherein the compaction density of the positive plate is 2.35g/cm 3 The compaction density of the negative plate is 1.50g/cm 3 ；
(4) Slitting and cutting piece
Dividing the rolled pole piece by a dividing machine, and cutting the positive pole piece and the negative pole piece into required sizes by a laser die cutting machine;
(5) Lamination sheet
Sequentially stacking the cut pole pieces, namely a negative pole piece, a diaphragm, a positive pole piece, a diaphragm, a negative pole piece, a diaphragm, a positive pole … … positive pole piece, a diaphragm and a negative pole piece to form an electric core;
(6) Assembly
The battery core is hot pressed under 1500N-2000N pressure, tab welding is carried out, the welded battery core is placed in an aluminum plastic film after pit punching for top sealing and side sealing, and baking and liquid injection (1 mo1/L LiPF) 6 Assembling into a soft package cell by processes of (EC+DMC) (volume ratio 1:1);
(7) Formation into
And (3) forming the soft-package battery cell at 45 ℃ 48 hours after liquid injection, wherein a formation system is specifically as follows: pre-charging to 3.3V with a current of 0.02-0.05C, then charging to 3.8V with a current of 0.2C to convert to constant voltage charging, terminating the current of 0.02-0.05C, discharging to 2.0V with 0.33C after full charging, and charging and discharging once with a current of 0.33C, wherein the discharge capacity of 0.33C is used as the formation capacity of the battery;
and (3) discharging gas in the soft package battery core after formation, hot-pressing and sealing the bag mouth of the aluminum plastic film packaging bag, the outer tab and the outer tab fixing sheet through adhesives, and finally carrying out capacity division, wherein the battery is charged and discharged twice under the condition of 25 ℃ at the current of 0.33 ℃, and the discharge capacity of 0.33C is used as the capacity division capacity of the battery.
2. Cycle performance test and low temperature performance test
The soft pack cells of examples 1 to 5 and comparative examples 1 to 4 were tested for cycle performance at room temperature at a current cycle of 5C for 200 weeks, and the soft pack cells of examples 1 to 5 and comparative examples 1 to 4 were also tested for cycle performance at room temperature at a current cycle of 30C for 1200 weeks, and the results are shown in table 2 and fig. 3 to 4.
The discharge capacities of the soft-pack cells of examples 1 to 5 and comparative examples 1 to 4 were measured at a discharge current of 0.33C and a temperature of-25 to 25℃, and the results are shown in table 2 and fig. 5.
Table 2 performance test of soft pack cells
As can be seen from table 2 and fig. 3, the capacity retention rates of the soft-pack cells of comparative examples 1-2 and examples 1-5 were 89.0%, 90.1%, 92.3%, 97.0%, 97.9%, 92.0%, 92.5% in this order at a current cycle of 5C for 200 weeks, and examples 1-5 exhibited superior cycle performance as compared to comparative examples 1-2; as can be seen from table 2 and fig. 4, the capacity retention rates of the soft-pack cells of comparative examples 1-2 and examples 1-5 were 64.5%, 72.8%, 81.3%, 82.1%, 83.2%, 82.0%, 81.5% in this order at a current cycle of 30C for 1000 weeks, indicating that examples 1-5 have better high rate cycle performance than comparative examples 1-2 due to the excellent conductivity of graphene nanotubes.
As can be seen from table 2 and fig. 5, the capacity retention rates of the soft-pack cells of comparative examples 1-2 and examples 1-5 were 58.0%, 60.1%, 62.0%, 65.8%, 66.1%, 62.5%, 61.6% in this order at-25 c, and the soft-pack cells of example 2 and example 3 had similar low temperature performance, indicating that the soft-pack cells of examples 1-5 had better low temperature performance than those of comparative examples 1-2.
As can be seen from comparison of examples 1, examples 4 to 5 and comparative examples 3 to 4, the soft-cap cell of comparative example 4 had a capacity retention rate of 200 weeks at a current of 5C, a capacity retention rate of 1000 weeks at a current of 30C, and a capacity retention rate of 0.33C, which were close to or identical to those of example 5, indicating that the increased multi-wall carbon nanotube of comparative example 4 did not significantly improve the cycle performance and low temperature performance of the soft-cap cell when the graphene nanotube was prepared, but increased the production cost of the soft-cap cell.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (12)
1. The preparation method of the graphene nanotube is characterized by comprising the following steps of:
mixing the multiwall carbon nanotubes, potassium nitrate and concentrated sulfuric acid, and stirring to form a mixed solution;
mixing potassium permanganate with the mixed solution, stirring, heating in a water bath, and preserving heat for a period of time to obtain a reaction solution after the reaction is completed; the mass ratio of the multiwall carbon nanotube to the potassium nitrate to the potassium permanganate is (1-1.2): 5:10;
and cooling the reaction liquid to room temperature, uniformly mixing the reaction liquid with a hydrogen peroxide solution and an ice-water mixture, and washing and centrifuging the reaction liquid to obtain the graphene nanotube.
2. The graphene nanotube according to claim 1, wherein the mass ratio of the multiwall carbon nanotube, potassium nitrate, potassium permanganate is 1:5:10.
3. the graphene nanotube according to claim 1, wherein the water bath temperature is 70-100 ℃ and the incubation time is 2-10 h.
4. The graphene nanotube according to any one of claims 1 to 3, wherein the volume ratio of the hydrogen peroxide solution to the ice-water mixture is 1:69, wherein the mass fraction of the hydrogen peroxide solution is 35%.
5. The positive electrode slurry is characterized by comprising a positive electrode active material, a binder, a solvent and the graphene nanotube according to any one of claims 1 to 4.
6. The positive electrode slurry according to claim 5, wherein the positive electrode active material comprises LiFePO 4 。
7. The positive electrode slurry of claim 5, wherein the binder comprises a fluoropolymer and the solvent comprises an amide-like compound.
8. The positive electrode slurry according to any one of claims 5 to 7, wherein the mass ratio of the positive electrode active material, the binder, and the graphene nanotubes is (80 to 90): 5: (5-15).
9. A positive electrode sheet, characterized in that the positive electrode sheet comprises a current collector and a positive electrode active material layer located on at least one surface of the current collector, and the positive electrode active material layer comprises the positive electrode slurry according to any one of claims 5 to 8.
10. A battery cell comprising the positive electrode sheet of claim 9.
11. The cell of claim 10, wherein the cell comprises any one of a soft pack cell, a square aluminum case cell, and a cylindrical cell.
12. An electronic device characterized by comprising a housing and the battery cell of any one of claims 10-11, the battery cell being located inside the housing.
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| CN106450174A (en) * | 2016-05-23 | 2017-02-22 | 重庆大学 | Preparation method for graphene nanobelt-lithium iron phosphate composite material |
| CN112290022A (en) * | 2020-10-20 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Lithium ion battery anode lithium supplement additive and preparation method and application thereof |
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| CN106450174A (en) * | 2016-05-23 | 2017-02-22 | 重庆大学 | Preparation method for graphene nanobelt-lithium iron phosphate composite material |
| CN112290022A (en) * | 2020-10-20 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Lithium ion battery anode lithium supplement additive and preparation method and application thereof |
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