CN111211304A - Long-cycle lithium ion battery and composite positive electrode active material, positive electrode slurry and positive electrode thereof - Google Patents
Long-cycle lithium ion battery and composite positive electrode active material, positive electrode slurry and positive electrode thereof Download PDFInfo
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- CN111211304A CN111211304A CN202010031888.0A CN202010031888A CN111211304A CN 111211304 A CN111211304 A CN 111211304A CN 202010031888 A CN202010031888 A CN 202010031888A CN 111211304 A CN111211304 A CN 111211304A
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- lithium ion
- ion battery
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- graphdine
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 102
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 65
- 239000010439 graphite Substances 0.000 claims abstract description 65
- -1 graphite alkyne Chemical class 0.000 claims abstract description 63
- 239000000654 additive Substances 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- 239000013543 active substance Substances 0.000 claims abstract description 8
- 239000002033 PVDF binder Substances 0.000 claims description 45
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 32
- 229910052744 lithium Inorganic materials 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 24
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 12
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 8
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 239000006183 anode active material Substances 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 229910012516 LiNi0.4Co0.2Mn0.4O2 Inorganic materials 0.000 claims description 2
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 claims description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 claims description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 21
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 112
- 238000003756 stirring Methods 0.000 description 92
- 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 27
- 239000006256 anode slurry Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- 230000014759 maintenance of location Effects 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 238000007790 scraping Methods 0.000 description 11
- 238000010586 diagram Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000010405 anode material Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- C01B32/20—Graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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 invention belongs to the technical field of lithium ion batteries, and particularly relates to a long-cycle lithium ion battery composite positive electrode active material which comprises a positive electrode active substance and a positive electrode additive; the positive electrode additive is graded graphite alkyne; the material comprises two or more of graphite alkyne A, graphite alkyne B and graphite alkyne C. The invention also provides a positive electrode material, a positive electrode slurry, a positive electrode and a lithium ion battery containing the composite positive electrode active material. By using the graded graphite alkyne mixture, the invention can be beneficial to the diffusion and transmission of lithium ions in and out of planes, and can obviously increase the cycle performance of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a lithium ion battery anode material.
Background
The appearance of lithium ion batteries with large discharge voltage and high energy density greatly promotes the miniaturization and light weight of electrical appliances such as mobile phones, notebook computers and the like. In recent years, the production capacity of lithium ion batteries has increased year by year, and the lithium ion batteries become the mainstream of power supplies of electronic devices and gradually expand into the fields of high-power systems such as electric automobiles, national defense industry, high-efficiency energy storage systems, satellites and the like. While research and development of new rechargeable batteries with high capacity and high energy density are being carried out, research and development of lithium ion batteries with long cycle performance are becoming more and more important.
At present, the cycle life of the digital lithium ion battery is about 300-3000 weeks, the cycle life of the power lithium ion battery is also different from that of the power lithium ion battery in 2000-3000 weeks, and unpredictable capacity loss and limited cycle life of the battery have great influence on the battery, so that researchers at home and abroad carry out deep research on the cycle life of the lithium ion battery so as to meet the practical application of the lithium ion battery in various fields.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a composite anode active material of a long-cycle lithium ion battery, and aims to innovatively use an anode additive and obviously improve the long-cycle effect of the lithium ion battery.
A second object of the present invention is to provide a positive electrode material comprising the composite positive electrode active material.
A third object of the present invention is to provide a positive electrode slurry containing the positive electrode material.
A fourth object of the present invention is to provide a positive electrode containing the positive electrode material.
A fifth object of the present invention is to provide a lithium ion battery including the positive electrode.
A long-cycle lithium ion battery composite anode active material comprises an anode active substance and an anode additive;
the positive electrode additive is graded graphite alkyne; wherein the graphite alkyne comprises two or more of graphite alkyne A, graphite alkyne B and graphite alkyne C;
wherein the particle size of D50 of the graphdine A is 1-30 nm; the particle size of D50 of the graphdine B is 31-100 nm; the particle size of the D50 of the graphdine C is 101-300 nm.
The invention innovatively discovers that the addition of the graphite alkyne in the grading mode into the positive electrode material of the lithium ion battery can unexpectedly and obviously improve the electrical property of lithium ions, and the cycle number of the lithium ion battery can be increased to more than 5000 times.
The research of the invention finds that the grading mode of the special grain diameter is the key point for realizing good effect of the grading mode on the aspect of long circulation of the lithium ion battery.
Further preferably, the particle size of the D50 of the graphdine A is 5-25 nm; the D50 particle size of the graphdine B is 50-90 nm; the particle size of the D50 of the graphdine C is 120-200 nm.
Preferably, the graded graphdiyne at least comprises graphdiyne A, and optionally comprises graphdiyne B and/or graphdiyne C.
Preferably, in the graded graphdiyne, the weight part of the graphdiyne A is 1-10 parts; the weight part of the graphdine B is less than or equal to 20 parts; the weight portion of the graphdine C is less than or equal to 10 portions.
Research also finds that on the basis of the control of the grading particle size, the grading mode and the grading proportion are further controlled, and the long-term cycle performance of the lithium ion battery is further improved.
Preferably, the graded graphdiyne comprises graphdiyne A and graphdiyne B; and the weight part of the graphdine A is 1-3 parts; the weight part of the graphdine B is 4-5 parts.
Preferably, the graded graphdiyne comprises graphdiyne A, graphdiyne B and graphdiyne C; and the weight part of the graphdine A is 1-3 parts; 4-17 parts of graphdine B; 3-5 parts of graphyne C.
Preferably, the positive active material is one or more of lithium cobaltate, lithium manganate, lithium nickel cobalt manganate and lithium nickel cobalt aluminate.
Preferably, the lithium nickel cobalt manganese oxide is LiNi1/3Co1/3Mn1/3O2、LiNi0.4Co0.2Mn0.4O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2One or more of them.
Research shows that the control of the content of the positive electrode additive is helpful for further improving the long cycle performance of the lithium ion battery.
Preferably, in the composite positive electrode active material, the weight part of the positive electrode active material is 80-99 parts, preferably 94-96 parts; the weight part of the positive electrode additive is 0.5-10 parts, preferably 0.5-2.5 parts.
The invention also provides a long-cycle lithium ion battery anode material which comprises the composite anode active material, and also comprises a binder and a conductive agent.
The adhesive can be any material with adhesive effect known to those skilled in the art, preferably polyvinylidene fluoride (PVDF).
Preferably, the conductive agent can be a substance having a conductive effect known to those skilled in the art, and is preferably one or more of SP, KS-6, SFG-6 and CNT.
Preferably, the content of the adhesive is 1-6 wt.%, preferably 2-4 wt.%; the content of the conductive agent is 0.5-4 wt.%, preferably 1.5-2.5 wt.%; the balance is the composite anode active material.
The invention also provides long-cycle lithium ion battery anode slurry which comprises the anode material and a solvent.
Preferably, the solvent may be a solvent known in the art to slurry the positive electrode material, preferably NMP.
Preferably, the solid content of the positive electrode slurry is 55-85%, and the viscosity is 3000-9000 mPa & s. Experiments show that when the solid content of the slurry is 55-85% and the viscosity is 3000-9000 mPas, the slurry is more suitable for improving the quality level of a coating process.
The preferable long-cycle lithium ion battery positive electrode slurry comprises a positive electrode active substance, a binder, a conductive agent, a solvent and a positive electrode additive, wherein the positive electrode additive is graphite alkyne, and the positive electrode active substance is one or more of lithium cobaltate, lithium manganate, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate; the adhesive is polyvinylidene fluoride (PVDF); the conductive agent is one or more of SP, KS-6, SFG-6 and CNT, and the solvent is N-methylpyrrolidone. The mass ratio of the positive active substance to the binder to the conductive agent to the additive is (80-99): (1.0-6.0): (0.5-4.0): (0.5 to 10.0).
The method for preparing the long-cycle lithium ion battery positive electrode slurry comprises the following steps:
the positive active substance, the binder, the conductive agent, the additive and the solvent are weighed according to the proportion, the binder is dissolved in the solvent accounting for 50-95% of the total amount of the organic solvent, a circulating water system of a stirring device is started, then the conductive agent and the additive are added for stirring, the materials are repeatedly stirred and scraped for a plurality of times, then the positive active substance is added for stirring and scraping, and finally the rest solvent is added for stirring until the solid content and the viscosity of the positive slurry reach the standard.
The invention also provides the long-cycle lithium ion battery anode, which comprises a current collector and the anode material compounded on the surface of the current collector.
The current collector may be any electrically conductive substrate known in the art, such as a metal substrate, a porous carbon material, and the like.
The invention also provides a long-cycle lithium ion battery which takes the anode as the anode.
Compared with the prior art, the invention has the following advantages:
1. the graphite alkyne is used as an additive and is added into a lithium ion positive electrode material, so that the long-acting cycle effect of the lithium ion battery can be improved.
2. The three-dimensional space structure with the synergistic effect is constructed by mixing graphite alkyne materials with different morphologies through the graded graphite, wherein the graphite alkyne A is a small-particle nanoscale planar carbon material with the particle size of 1-30nm, the graphite alkyne B is a medium-particle nanoscale planar carbon material with the particle size of 31-100nm, and the graphite alkyne C is a large-particle nanoscale planar carbon material with the particle size of 101-300 nm. The three materials with different sizes are mixed together in a grading way and mutually perform synergistic action, so that the electronic conductivity and lithium storage sites of the cathode material are increased, and the unique structure of the cathode material is favorable for the diffusion and transmission of lithium ions in and out of planes, so that the prepared battery has very excellent cycle stability. The long-acting cycle number of the added lithium ion battery material can be increased to more than 5000 circles.
Drawings
FIG. 1 is a combination graph of cycle life curves of examples 1 to 5 and comparative examples 1 to 5;
FIG. 2 is a graph showing cycle life curves of examples 1 to 5 and comparative examples 1 to 5, respectively.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The graphdiyne used was purchased from Jiangsu Xiancheng nanomaterial science and technology limited.
Example 1
A preparation method of long-cycle lithium ion battery anode slurry comprises the following steps:
(1) mixing 0.2kg of graphyne with the particle size of 10nm, 0.5kg of graphyne with the particle size of 50nm and 0.3kg of graphyne with the particle size of 120nm together to obtain 1kg of graphyne graded mixture;
(2) 47kg of lithium cobaltate, 47kg of lithium nickel cobalt manganese oxide, 3kg of polyvinylidene fluoride PVDF, 1kg of SP, 1kg of KS-6, 1kg of a graphite alkyne gradation mixture and 45kg of N-methylpyrrolidone NMP are weighed and sieved respectively.
(3) Adding all polyvinylidene fluoride (PVDF) into a stirring barrel filled with 36kg of N-methylpyrrolidone NMP accounting for 80% of the total amount of N-methylpyrrolidone NMP, and stirring for 30min, wherein the rotation speed of the stirrer is 1000rpm, and the revolution speed of the stirrer is 50 rpm.
(4) And then adding SP and KS-6 into the stirring barrel at the same time, stirring for 20min, wherein the rotation speed of the stirrer is 1000rpm, the revolution speed of the stirrer is 40rpm, adding the graphite alkyne graded mixture twice, and stirring for 10min respectively, wherein the rotation speed of the stirrer is 1200rpm, and the revolution speed of the stirrer is 50 rpm.
(5) Then adding 6.75kg of N-methylpyrrolidone NMP which accounts for 15% of the total amount of the N-methylpyrrolidone into a stirring barrel, adding lithium cobaltate and nickel cobalt lithium manganate twice, stirring for 20min after adding the lithium cobaltate and the nickel cobalt lithium manganate for the first time, scraping materials on the periphery after stopping, stirring for 40min after adding the lithium cobaltate and the nickel cobalt lithium manganate for the second time, wherein the rotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
(6) And finally, adding the rest N-methylpyrrolidone NMP step by step and stirring for 10min, wherein the autorotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
And (3) measuring the solid content and the viscosity of a small amount of the lithium ion battery anode slurry prepared by the steps, wherein the solid content is 69%, and the viscosity is 4500 mPa.
The lithium ion battery anode slurry prepared in the example 1 is prepared into an anode plate according to the process of the soft package type lithium ion battery 75065190-9Ah, and is prepared into a battery according to the process of the soft package type lithium ion battery 75065190-9 Ah. The manufactured battery is charged by using a 1C constant current and a constant voltage until the cut-off voltage is 4.2V, the cut-off current is 180mA, and discharged by using a 1C constant current to 2.75V, and the cycle life curve diagram is shown in figure 1, and as can be seen from figure 1, the capacity retention rate is still over 90 percent when the battery is cycled for about 5000 times, and the cycle life is very excellent.
Example 2
A preparation method of long-cycle lithium ion battery anode slurry is disclosed, in the example, only a graphite alkyne graded mixture with two particle sizes (graphite alkyne A and graphite alkyne B) is added, and the preparation method comprises the following steps:
(1) 0.1kg of graphdiyne with the particle size of 20nm and 0.4kg of graphdiyne with the particle size of 90nm are mixed together to obtain 0.5kg of graphdiyne graded mixture;
(2) 32kg of lithium nickel cobalt aluminate, 64kg of lithium manganate, 2kg of polyvinylidene fluoride PVDF, 1kg of SP, 0.5kg of KS-6, 0.5kg of a graphdine-graded mixture and 40kg of N-methylpyrrolidone NMP were weighed and the powder materials were sieved separately.
(3) Adding all polyvinylidene fluoride (PVDF) into a stirring barrel filled with 24kg of N-methylpyrrolidone NMP accounting for 60% of the total amount of the N-methylpyrrolidone NMP, and stirring for 50min, wherein the rotation speed of the stirrer is 1200rpm, and the revolution speed of the stirrer is 40 rpm.
(4) And then adding SP and KS-6 into the stirring barrel simultaneously, stirring for 30min, wherein the rotation speed of the stirrer is 1200rpm, the revolution speed of the stirrer is 50rpm, adding the graphite alkyne graded mixture for three times, and stirring for 10min respectively, wherein the rotation speed of the stirrer is 1000rpm, and the revolution speed of the stirrer is 45 rpm.
(5) Then adding 14kg of N-methylpyrrolidone NMP which accounts for 35% of the total amount of the N-methylpyrrolidone into a stirring barrel, adding the lithium nickel cobalt aluminate and the lithium manganate twice, stirring for 30min after adding the lithium nickel cobalt aluminate and the lithium manganate for the first time, scraping materials at the periphery after stopping, stirring for 30min after adding the lithium nickel cobalt aluminate and the lithium manganate for the second time, wherein the rotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
(6) And finally, adding the rest N-methylpyrrolidone NMP step by step and stirring for 20min, wherein the rotation speed of the stirrer is 1800rpm, and the revolution speed of the stirrer is 50 rpm.
And (3) measuring the solid content and the viscosity of a small amount of the lithium ion battery anode slurry prepared by the steps, wherein the solid content is 71% and the viscosity is 5500mPa & s.
The lithium ion battery anode slurry prepared in the example 2 is prepared into an anode plate according to the process of the soft package type lithium ion battery 75065190-9Ah, and is prepared into a battery according to the process of the soft package type lithium ion battery 75065190-9 Ah. The manufactured battery is charged by using a 1C constant current and a constant voltage until the cut-off voltage is 4.2V, the cut-off current is 180mA, and discharged by using a 1C constant current to 2.75V, and the cycle life curve diagram is shown in figure 1, and as can be seen from figure 1, the battery has the capacity retention rate of more than 90% and the cycle life is very excellent after being cycled for about 5000 times, and is similar to that of the battery in example 1.
Example 3
A preparation method of long-cycle lithium ion battery anode slurry comprises the following steps:
(1) mixing 0.3kg of graphyne with the particle size of 25nm, 1.7kg of graphyne with the particle size of 70nm and 0.5kg of graphyne with the particle size of 200nm together to obtain 2.5kg of graphyne graded mixture;
(2) 95kg of nickel cobalt lithium manganate, 1.5kg of polyvinylidene fluoride PVDF, 0.5kg of SP, 0.5kg of KS-6, 2.5kg of a graphdine-graded mixture and 50kg of N-methylpyrrolidone NMP are weighed and sieved respectively.
(3) And adding all polyvinylidene fluoride (PVDF) into a stirring barrel filled with 37.5kg of N-methylpyrrolidone NMP accounting for 75% of the total amount of N-methylpyrrolidone NMP, and stirring for 50min, wherein the rotation speed of the stirrer is 1200rpm, and the revolution speed of the stirrer is 50 rpm.
(4) And then adding SP and KS-6 into the stirring barrel simultaneously, stirring for 20min, wherein the rotation speed of the stirrer is 1500rpm, the revolution speed of the stirrer is 50rpm, then adding the graphite alkyne graded mixture, and stirring for 30min respectively, wherein the rotation speed of the stirrer is 1200rpm, and the revolution speed of the stirrer is 50 rpm.
(5) Then adding 11kg of N-methylpyrrolidone NMP which accounts for 22% of the total amount of the N-methylpyrrolidone into a stirring barrel, adding the nickel cobalt lithium manganate twice, stirring for 20min after adding the nickel cobalt lithium manganate for the first time, scraping materials on the periphery after stopping, stirring for 20min after adding the nickel cobalt lithium manganate for the second time, wherein the autorotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
(6) And finally, adding the rest N-methylpyrrolidone NMP step by step and stirring for 40min, wherein the autorotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
And (3) measuring the solid content and the viscosity of a small amount of the lithium ion battery anode slurry prepared by the steps, and measuring that the solid content is 67% and the viscosity is 3000mPa & s.
The lithium ion battery positive electrode slurry prepared in the embodiment 3 is prepared into a positive plate according to the process of the soft package type lithium ion battery 75065190-9Ah, and is prepared into a battery according to the process of the soft package type lithium ion battery 75065190-9 Ah. The manufactured battery is charged by using a 1C constant current and a constant voltage until the cut-off voltage is 4.2V, the cut-off current is 180mA, and discharged by using a 1C constant current to 2.75V, and the cycle life curve diagram is shown in figure 1, and as can be seen from figure 1, the battery has the capacity retention rate of more than 90% and the cycle life is very excellent after being cycled for about 5000 times, and is similar to that of the battery in the embodiment 1 and the embodiment 2.
Example 4
A preparation method of long-cycle lithium ion battery anode slurry comprises the following steps:
(1) mixing 2kg of graphdiyne with the particle size of 15nm, 6kg of graphdiyne with the particle size of 60nm and 2kg of graphdiyne with the particle size of 140nm to obtain 10kg of graphdiyne graded mixture;
(2) 68kg of nickel cobalt lithium manganate, 17kg of lithium manganate, 2kg of polyvinylidene fluoride PVDF, 1.5kg of SP, 1.5kg of KS-6, 10kg of a graphite alkyne gradation mixture and 55kg of N-methylpyrrolidone NMP are weighed and sieved respectively.
(3) And adding all polyvinylidene fluoride (PVDF) into a stirring barrel filled with 38.5kg of N-methylpyrrolidone NMP accounting for 70% of the total amount of the N-methylpyrrolidone NMP, and stirring for 50min, wherein the rotation speed of the stirrer is 1200rpm, and the revolution speed of the stirrer is 50 rpm.
(4) And then adding SP and KS-6 into the stirring barrel simultaneously, stirring for 20min, wherein the rotation speed of the stirrer is 1500rpm, the revolution speed of the stirrer is 50rpm, then adding the graphite alkyne graded mixture, and stirring for 30min respectively, wherein the rotation speed of the stirrer is 1200rpm, and the revolution speed of the stirrer is 50 rpm.
(5) Then adding 13.75kg of N-methylpyrrolidone NMP accounting for 25 percent of the total amount of the N-methylpyrrolidone into a stirring barrel, adding the nickel cobalt lithium manganate twice, stirring for 20min after adding the nickel cobalt lithium manganate for the first time, scraping materials on the periphery after stopping, stirring for 20min after adding the nickel cobalt lithium manganate for the second time, wherein the autorotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
(6) And finally, adding the rest N-methylpyrrolidone NMP step by step and stirring for 40min, wherein the autorotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
And (3) measuring the solid content and the viscosity of a small amount of the lithium ion battery anode slurry prepared by the steps, wherein the solid content is 64.5%, and the viscosity is 3500mPa & s.
The lithium ion battery positive electrode slurry prepared in the embodiment 4 is manufactured into a positive plate according to the process of the soft package type lithium ion battery 75065190-9Ah, and is manufactured into a battery according to the process of the soft package type lithium ion battery 75065190-9 Ah. The manufactured battery is charged by using a 1C constant current and a constant voltage until the cut-off voltage is 4.2V, the cut-off current is 180mA, and discharged by using a 1C constant current to 2.75V, and the cycle life curve diagram is shown in figure 1, and as can be seen from figure 1, the battery has the capacity retention rate of more than 90% and the cycle life is very excellent after being cycled for about 5000 times, and is similar to the battery in the embodiment 1, the embodiment 2 and the embodiment 3.
Example 5
A preparation method of long-cycle lithium ion battery anode slurry is disclosed, in the example, only a graphite alkyne graded mixture with two particle sizes (graphite alkyne B and graphite alkyne C) is added, and the preparation method comprises the following steps:
(1) mixing 3kg of graphite alkyne with the particle size of 70nm and 3kg of graphite alkyne with the particle size of 150nm together to obtain 6kg of graphite alkyne graded mixture;
(2) 88kg of lithium cobaltate, 3.5kg of PVDF, 1kg of SP, 1.5kg of KS-6, 6kg of a graphite alkyne gradation mixture and 60kg of NMP were weighed and the powder materials were sieved separately.
(3) Adding all polyvinylidene fluoride (PVDF) into a stirring barrel filled with 45kg of N-methylpyrrolidone NMP accounting for 75% of the total amount of N-methylpyrrolidone NMP, and stirring for 30min, wherein the rotation speed of the stirrer is 1000rpm, and the revolution speed of the stirrer is 50 rpm.
(4) And then adding SP and KS-6 into the stirring barrel at the same time, stirring for 20min, wherein the rotation speed of the stirrer is 1000rpm, the revolution speed of the stirrer is 40rpm, adding the graphite alkyne graded mixture twice, and stirring for 10min respectively, wherein the rotation speed of the stirrer is 1200rpm, and the revolution speed of the stirrer is 50 rpm.
(5) And then adding 12kg of N-methylpyrrolidone NMP (N-methylpyrrolidone) accounting for 20% of the total amount of the N-methylpyrrolidone into the stirring barrel, adding lithium cobaltate and lithium nickel cobalt manganese oxide twice, stirring for 20min after adding the lithium cobaltate and the lithium nickel cobalt manganese oxide for the first time, scraping materials on the periphery after stopping, stirring for 40min after adding the lithium cobaltate and the lithium nickel cobalt manganese oxide for the second time, wherein the rotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
(6) And finally, adding the rest N-methylpyrrolidone NMP step by step and stirring for 10min, wherein the autorotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
And (3) measuring the solid content and the viscosity of a small amount of the lithium ion battery anode slurry prepared by the steps, and measuring that the solid content is 62.5% and the viscosity is 4000mPa & s.
The lithium ion battery anode slurry prepared in the example 5 is prepared into an anode plate according to the process of the soft package type lithium ion battery 75065190-9Ah, and is prepared into a battery according to the process of the soft package type lithium ion battery 75065190-9 Ah. The manufactured battery is charged by using a 1C constant current and a constant voltage until the cut-off voltage is 4.2V, the cut-off current is 180mA, and discharged by using a 1C constant current until the cut-off voltage is 2.75V, and the cycle life curve chart is shown in figure 1, and as can be seen from figure 1, the capacity retention rate is about 88% and the cycle life is good and is slightly lower than that of the battery in example 1, example 2, example 3 and example 4 after the battery is cycled for about 5000 times.
Comparative example 1
In the example, no graphdiyne was added, and the remaining preparation method and steps were the same as in example 1, and were carried out as follows:
(1) 47kg of lithium cobaltate, 47kg of lithium nickel cobalt manganese oxide, 3kg of polyvinylidene fluoride PVDF, 1kg of SP, 1kg of KS-6 and 45kg of N-methylpyrrolidone NMP are weighed and sieved respectively.
(2) Adding all polyvinylidene fluoride (PVDF) into a stirring barrel filled with 36kg of N-methylpyrrolidone NMP accounting for 80% of the total amount of N-methylpyrrolidone NMP, and stirring for 30min, wherein the rotation speed of the stirrer is 1000rpm, and the revolution speed of the stirrer is 50 rpm.
(3) Then, SP and KS-6 were added to the stirring tank at the same time, and stirred for 20min at a rotation speed of 1000rpm and a revolution speed of 40 rpm.
(4) Then adding 6.75kg of N-methylpyrrolidone NMP which accounts for 15% of the total amount of the N-methylpyrrolidone into a stirring barrel, adding lithium cobaltate and nickel cobalt lithium manganate twice, stirring for 20min after adding the lithium cobaltate and the nickel cobalt lithium manganate for the first time, scraping materials on the periphery after stopping, stirring for 40min after adding the lithium cobaltate and the nickel cobalt lithium manganate for the second time, wherein the rotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
(5) And finally, adding the rest N-methylpyrrolidone NMP step by step and stirring for 10min, wherein the autorotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
And (3) measuring the solid content and the viscosity of a small amount of the lithium ion battery anode slurry prepared by the steps, wherein the solid content is 69%, and the viscosity is 4500 mPa.
And (3) preparing the lithium ion battery anode slurry prepared in the comparative example 1 into an anode plate according to the process of the soft package type lithium ion battery 75065190-9Ah, and preparing into a battery according to the process of the soft package type lithium ion battery 75065190-9 Ah. The manufactured battery is charged by using a 1C constant current and constant voltage until the cut-off voltage is 4.2V, the cut-off current is 180mA, and discharged by using a 1C constant current to 2.75V, and a cycle life curve chart is shown in figure 1, and as can be seen from figure 1, the battery has the capacity retention rate lower than 80% and the cycle life is poor when the battery is cycled to about 2100 times.
Comparative example 2
In the example, the preparation method and the steps are the same as those of the example 1 except that the graphdine graded mixture is not added and only the graphdine B with one particle size is added, and the method comprises the following steps:
(1) 47kg of lithium cobaltate, 47kg of lithium nickel cobalt manganese oxide, 3kg of polyvinylidene fluoride PVDF, 1kg of SP, 1kg of KS-6, 1kg of graphite alkyne (particle size 50nm), 45kg of N-methylpyrrolidone NMP were weighed and the powder materials were sieved separately.
(2) Adding all polyvinylidene fluoride (PVDF) into a stirring barrel filled with 36kg of N-methylpyrrolidone NMP accounting for 80% of the total amount of N-methylpyrrolidone NMP, and stirring for 30min, wherein the rotation speed of the stirrer is 1000rpm, and the revolution speed of the stirrer is 50 rpm.
(3) And then adding SP and KS-6 into the stirring barrel simultaneously, stirring for 20min, wherein the rotation speed of the stirrer is 1000rpm, the revolution speed of the stirrer is 40rpm, adding the graphdine twice, and stirring for 10min respectively, wherein the rotation speed of the stirrer is 1200rpm, and the revolution speed of the stirrer is 50 rpm.
(4) Then adding 6.75kg of N-methylpyrrolidone NMP which accounts for 15% of the total amount of the N-methylpyrrolidone into a stirring barrel, adding lithium cobaltate and nickel cobalt lithium manganate twice, stirring for 20min after adding the lithium cobaltate and the nickel cobalt lithium manganate for the first time, scraping materials on the periphery after stopping, stirring for 40min after adding the lithium cobaltate and the nickel cobalt lithium manganate for the second time, wherein the rotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
(5) And finally, adding the rest N-methylpyrrolidone NMP step by step and stirring for 10min, wherein the autorotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
And (3) measuring the solid content and the viscosity of a small amount of the lithium ion battery anode slurry prepared by the steps, wherein the solid content is 69%, and the viscosity is 4500 mPa.
And (3) preparing the lithium ion battery anode slurry prepared in the comparative example 2 into an anode plate according to the process of the soft package type lithium ion battery 75065190-9Ah, and preparing into a battery according to the process of the soft package type lithium ion battery 75065190-9 Ah. The manufactured battery is charged by using a 1C constant current and a constant voltage until the cut-off voltage is 4.2V, the cut-off current is 180mA, and discharged by using a 1C constant current to 2.75V, and the cycle life curve diagram is shown in figure 1, and as can be seen from figure 1, the battery circulates to about 3800 times, the capacity retention rate is lower than 80%, and the cycle life is general.
Comparative example 3
In the example, the preparation method and the steps are the same as those of the example 1 except that the graphite alkyne graded mixture is not added, only graphite alkyne C with one particle size is added, and the preparation method comprises the following steps:
(1) 47kg of lithium cobaltate, 47kg of lithium nickel cobalt manganese oxide, 3kg of polyvinylidene fluoride PVDF, 1kg of SP, 1kg of KS-6, 1kg of graphite alkyne (particle size of 120nm), 45kg of N-methylpyrrolidone NMP were weighed and the respective powder materials were sieved.
(2) Adding all polyvinylidene fluoride (PVDF) into a stirring barrel filled with 36kg of N-methylpyrrolidone NMP accounting for 80% of the total amount of N-methylpyrrolidone NMP, and stirring for 30min, wherein the rotation speed of the stirrer is 1000rpm, and the revolution speed of the stirrer is 50 rpm.
(3) And then adding SP and KS-6 into the stirring barrel simultaneously, stirring for 20min, wherein the rotation speed of the stirrer is 1000rpm, the revolution speed of the stirrer is 40rpm, adding the graphdine twice, and stirring for 10min respectively, wherein the rotation speed of the stirrer is 1200rpm, and the revolution speed of the stirrer is 50 rpm.
(4) Then adding 6.75kg of N-methylpyrrolidone NMP which accounts for 15% of the total amount of the N-methylpyrrolidone into a stirring barrel, adding lithium cobaltate and nickel cobalt lithium manganate twice, stirring for 20min after adding the lithium cobaltate and the nickel cobalt lithium manganate for the first time, scraping materials on the periphery after stopping, stirring for 40min after adding the lithium cobaltate and the nickel cobalt lithium manganate for the second time, wherein the rotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
(5) And finally, adding the rest N-methylpyrrolidone NMP step by step and stirring for 10min, wherein the autorotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
And (3) measuring the solid content and the viscosity of a small amount of the lithium ion battery anode slurry prepared by the steps, wherein the solid content is 69%, and the viscosity is 4500 mPa.
And (3) preparing the lithium ion battery anode slurry prepared in the comparative example 3 into an anode plate according to the process of the soft package type lithium ion battery 75065190-9Ah, and preparing into a battery according to the process of the soft package type lithium ion battery 75065190-9 Ah. The manufactured battery is charged by using a 1C constant current and a constant voltage until the cut-off voltage is 4.2V, the cut-off current is 180mA, and discharged by using a 1C constant current to 2.75V, and the cycle life curve diagram is shown in figure 1, and as can be seen from figure 1, the battery circulates to about 3800 times, the capacity retention rate is lower than 80%, and the cycle life is general.
Comparative example 4
In the example, a nanoscale graphite alkyne and micron graphite alkyne graded mixture is added, and the rest preparation method and steps are the same as those in example 1, and the method comprises the following steps:
(1) mixing 0.5kg of graphite alkyne with the particle size of 50nm and 0.5kg of graphite alkyne with the particle size of 6mm together to obtain 1kg of graphite alkyne graded mixture;
(2) 47kg of lithium cobaltate, 47kg of lithium nickel cobalt manganese oxide, 3kg of polyvinylidene fluoride PVDF, 1kg of SP, 1kg of KS-6, 1kg of graphdine and 45kg of N-methylpyrrolidone NMP are weighed and sieved respectively.
(3) Adding all polyvinylidene fluoride (PVDF) into a stirring barrel filled with 36kg of N-methylpyrrolidone NMP accounting for 80% of the total amount of N-methylpyrrolidone NMP, and stirring for 30min, wherein the rotation speed of the stirrer is 1000rpm, and the revolution speed of the stirrer is 50 rpm.
(4) And then adding SP and KS-6 into the stirring barrel simultaneously, stirring for 20min, wherein the rotation speed of the stirrer is 1000rpm, the revolution speed of the stirrer is 40rpm, adding the graphdine twice, and stirring for 10min respectively, wherein the rotation speed of the stirrer is 1200rpm, and the revolution speed of the stirrer is 50 rpm.
(5) Then adding 6.75kg of N-methylpyrrolidone NMP which accounts for 15% of the total amount of the N-methylpyrrolidone into a stirring barrel, adding lithium cobaltate and nickel cobalt lithium manganate twice, stirring for 20min after adding the lithium cobaltate and the nickel cobalt lithium manganate for the first time, scraping materials on the periphery after stopping, stirring for 40min after adding the lithium cobaltate and the nickel cobalt lithium manganate for the second time, wherein the rotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
(6) And finally, adding the rest N-methylpyrrolidone NMP step by step and stirring for 10min, wherein the autorotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
And (3) measuring the solid content and the viscosity of a small amount of the lithium ion battery anode slurry prepared by the steps, wherein the solid content is 69%, and the viscosity is 4500 mPa.
And (3) preparing the lithium ion battery anode slurry prepared in the comparative example 4 into an anode plate according to the process of the soft package type lithium ion battery 75065190-9Ah, and preparing into a battery according to the process of the soft package type lithium ion battery 75065190-9 Ah. The manufactured battery is charged by using a 1C constant current and a constant voltage until the cut-off voltage is 4.2V, the cut-off current is 180mA, and discharged by using a 1C constant current to 2.75V, and the cycle life curve diagram is shown in figure 1, and as can be seen from figure 1, the battery has the capacity retention rate lower than 80% and the cycle life is poor when the battery is cycled to about 2700 times.
Comparative example 5
In this example, 3 kinds of nanoscale graphite alkyne gradation mixtures were added, but the ratio was not controlled within the desired range, and the other preparation methods and steps were the same as in example 1, and the following steps were performed:
(1) mixing 5kg of graphdiyne with the particle size of 10nm, 1kg of graphdiyne with the particle size of 50nm and 6kg of graphdiyne with the particle size of 120nm together to obtain 12kg of graphdiyne graded mixture;
(2) 41.5kg of lithium cobaltate, 41.5kg of lithium nickel cobalt manganese oxide, 3kg of polyvinylidene fluoride PVDF, 1kg of SP, 1kg of KS-6, 12kg of graphdine and 45kg of N-methylpyrrolidone NMP are weighed and sieved respectively.
(3) Adding all polyvinylidene fluoride (PVDF) into a stirring barrel filled with 36kg of N-methylpyrrolidone NMP accounting for 80% of the total amount of N-methylpyrrolidone NMP, and stirring for 30min, wherein the rotation speed of the stirrer is 1000rpm, and the revolution speed of the stirrer is 50 rpm.
(4) And then adding SP and KS-6 into the stirring barrel simultaneously, stirring for 20min, wherein the rotation speed of the stirrer is 1000rpm, the revolution speed of the stirrer is 40rpm, adding the graphdine twice, and stirring for 10min respectively, wherein the rotation speed of the stirrer is 1200rpm, and the revolution speed of the stirrer is 50 rpm.
(5) Then adding 6.75kg of N-methylpyrrolidone NMP which accounts for 15% of the total amount of the N-methylpyrrolidone into a stirring barrel, adding lithium cobaltate and nickel cobalt lithium manganate twice, stirring for 20min after adding the lithium cobaltate and the nickel cobalt lithium manganate for the first time, scraping materials on the periphery after stopping, stirring for 40min after adding the lithium cobaltate and the nickel cobalt lithium manganate for the second time, wherein the rotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
(6) And finally, adding the rest N-methylpyrrolidone NMP step by step and stirring for 10min, wherein the autorotation speed of the stirrer is 1500rpm, and the revolution speed of the stirrer is 50 rpm.
And (3) measuring the solid content and the viscosity of a small amount of the lithium ion battery anode slurry prepared by the steps, wherein the solid content is 69%, and the viscosity is 4500 mPa.
And (3) preparing the lithium ion battery anode slurry prepared in the comparative example 5 into an anode plate according to the process of the soft package type lithium ion battery 75065190-9Ah, and preparing into a battery according to the process of the soft package type lithium ion battery 75065190-9 Ah. The manufactured battery is charged by using a 1C constant current and a constant voltage until the cut-off voltage is 4.2V, the cut-off current is 180mA, and discharged by using a 1C constant current until the cut-off voltage is 2.75V, and a cycle life curve chart is shown in figure 1, and as can be seen from figure 1, the battery circulates to about 3500 times, the capacity retention rate is lower than 80%, and the cycle life is general.
FIG. 1 is a cycle life graph of lithium ion batteries manufactured from the positive electrode pastes prepared by the methods of example 1, example 2, example 3, example 4, example 5, comparative example 1, comparative example 2, comparative example 3, comparative example 4 and comparative example 5. As can be seen from fig. 1, the lithium ion batteries (example 1, example 3 and example 4) added with 3 nanoscale graphite alkyne-graded mixtures have excellent cycle performance, and the capacity retention rate is still kept above 90% after 5000 cycles; the lithium ion battery (example 2) added with 2 nanoscale graphite alkyne graded mixtures (graphite alkyne A and graphite alkyne B) has excellent cycle performance, and the capacity retention rate is still kept above 90% after 5000 cycles; the lithium ion battery (example 5) added with 2 nanoscale graphite alkyne graded mixtures (graphite alkyne B and graphite alkyne C) has good cycle performance, and the capacity retention rate is still kept at 88% after 5000 cycles; the lithium ion battery without the graphite alkyne (comparative example 1) has poor cycle performance, and the capacity retention rate is lower than 80% after 2100-week cycle; the lithium ion battery (comparative example 2 and comparative example 3) which is not added with the graphite alkyne grading mixture and is only added with one graphite alkyne with the nano particle size has general cycle performance, and the capacity retention rate is below 80 percent after 3800 cycles; in addition, the lithium ion battery (comparative example 4) added with the nanoscale graphite alkyne and micron graphite alkyne graded mixture has poor cycle performance, and the capacity retention rate is below 80% after 2700 cycles; and 3 kinds of nanoscale graphite alkyne graded mixtures are added, but the proportion range of each component is not controlled in the required range, and the prepared lithium ion battery (comparative example 5) has the cycle performance generally, and the capacity retention rate is below 80% after less than 3500 cycles. Therefore, the addition of 2 or 3 nanoscale graphite alkyne graded mixtures can obviously improve the cycle performance of the lithium ion battery.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A long-cycle lithium ion battery composite anode active material is characterized by comprising an anode active substance and an anode additive;
the positive electrode additive is graded graphite alkyne; wherein the graphite alkyne comprises two or more of graphite alkyne A, graphite alkyne B and graphite alkyne C;
wherein the particle size of D50 of the graphdine A is 1-30 nm; the particle size of D50 of the graphdine B is 31-100 nm; the particle size of the D50 of the graphdine C is 101-300 nm.
2. The long-cycle lithium ion battery composite positive active material of claim 1, wherein the particle size of the graphite alkyne a, D50, is 5-25 nm; the D50 particle size of the graphdine B is 50-90 nm; the particle size of the D50 of the graphdine C is 120-200 nm.
3. The long-cycle lithium ion battery composite positive electrode active material of claim 1, wherein the graded graphdiyne comprises at least graphdiyne a, optionally graphdiyne B and/or graphdiyne C;
preferably, the weight part of the graphdine A is 1-10 parts; the weight part of the graphdine B is less than or equal to 20 parts; the weight part of the graphdine C is less than or equal to 10 parts;
preferably, the graded graphdiyne comprises graphdiyne A and graphdiyne B; and the weight part of the graphdine A is 1-3 parts; 4-5 parts of graphyne B;
preferably, the graded graphdiyne comprises graphdiyne A, graphdiyne B and graphdiyne C; and the weight part of the graphdine A is 1-3 parts; 4-17 parts of graphdine B; 3-5 parts of graphyne C.
4. The long-cycle lithium ion battery composite positive active material of claim 1, wherein the positive active material is one or more of lithium cobaltate, lithium manganate, lithium nickel cobalt aluminate;
preferably, the lithium nickel cobalt manganese oxide is LiNi1/3Co1/3Mn1/3O2、LiNi0.4Co0.2Mn0.4O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2One or more of them.
5. The composite positive active material for the long-cycle lithium ion battery according to claim 1, wherein the weight part of the positive active material in the composite positive active material is preferably 80 to 99 parts; the weight part of the positive electrode additive is 0.5-10 parts.
6. A long-cycle lithium ion battery positive electrode material, which comprises the composite positive electrode active material according to any one of claims 1 to 5, and further comprises a binder and a conductive agent.
7. The long-cycle lithium ion battery positive electrode material of claim 6, wherein the binder is polyvinylidene fluoride (PVDF);
the conductive agent is one or more of SP, KS-6, SFG-6 and CNT;
preferably, the content of the adhesive is 1-6 wt.%; the content of the conductive agent is 0.5-4 wt.%.
8. A long-cycle lithium ion battery positive electrode slurry comprising the positive electrode material according to claim 7 or 8 and a solvent;
preferably, the solvent is NMP;
preferably, the solid content of the positive electrode slurry is 55-85%, and the viscosity is 3000-9000 mPa & s.
9. The long-cycle lithium ion battery positive electrode according to claim 8, comprising a current collector and the positive electrode material according to claim 6 or 7 compounded on the surface of the current collector.
10. A long-cycle lithium ion battery comprising the positive electrode according to claim 9 as a positive electrode.
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| CN108511754A (en) * | 2017-05-02 | 2018-09-07 | 万向二三股份公司 | A kind of negative electrode slurry |
| CN110651386A (en) * | 2017-10-30 | 2020-01-03 | 株式会社Lg化学 | Negative electrode active material for electrochemical device, negative electrode comprising the same, and electrochemical device comprising the same |
| CN110224131A (en) * | 2019-07-03 | 2019-09-10 | 珠海冠宇电池有限公司 | A kind of lithium ion battery and preparation method thereof |
| CN110660965A (en) * | 2019-08-29 | 2020-01-07 | 孚能科技(赣州)股份有限公司 | Negative plate and preparation method thereof, lithium ion battery and preparation method and application thereof |
| CN110600702A (en) * | 2019-09-18 | 2019-12-20 | 上海应用技术大学 | Composite material for core-shell structure secondary battery using waste diaphragm as raw material, preparation and application thereof |
| CN110690409A (en) * | 2019-10-17 | 2020-01-14 | 朱虎 | Preparation method of natural graphite-based negative electrode |
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