CN114914421B - Polymer-coated natural graphite anode material and preparation method and application thereof - Google Patents
Polymer-coated natural graphite anode material and preparation method and application thereof Download PDFInfo
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- CN114914421B CN114914421B CN202210551737.7A CN202210551737A CN114914421B CN 114914421 B CN114914421 B CN 114914421B CN 202210551737 A CN202210551737 A CN 202210551737A CN 114914421 B CN114914421 B CN 114914421B
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- 229910021382 natural graphite Inorganic materials 0.000 title claims abstract description 101
- 229920000642 polymer Polymers 0.000 title claims abstract description 89
- 239000010405 anode material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 53
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 45
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 45
- 239000011247 coating layer Substances 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- 239000007773 negative electrode material Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000000725 suspension Substances 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 28
- 238000001704 evaporation Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 239000011268 mixed slurry Substances 0.000 claims description 15
- 229920002401 polyacrylamide Polymers 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 239000007966 viscous suspension Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 17
- 238000000576 coating method Methods 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910002804 graphite Inorganic materials 0.000 abstract description 7
- 239000010439 graphite Substances 0.000 abstract description 7
- 239000013589 supplement Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/366—Composites as layered products
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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 discloses a polymer-coated natural graphite anode material, a preparation method and application thereof, wherein the anode material comprises natural graphite, and a polymer coating layer and a lithium salt coating layer which are uniformly coated on the surface of the natural graphite, wherein the weight ratio of the natural graphite to the polymer to the lithium salt is 300: (1.2-5.0): (0.8-4.0). According to the negative electrode material, the stable artificial SEI film is formed on the surface of the natural graphite through the polymer, the polymer SEI film is firm and flexible, the problem that naturally generated inorganic SEI is unstable is avoided, the cycle performance of the graphite is improved, the polymer coating can also reduce the specific surface of the natural graphite, further the active site is reduced, the first effect is improved, the lithium salt coating layer is added on the basis of the polymer, the lithium ions consumed by supplement can be added, the first effect can be further improved, and the overall polymer coated natural graphite negative electrode material has the advantages of high first effect, high capacity and the like.
Description
Technical Field
The invention relates to the technical field of new energy lithium ion battery negative electrode materials, in particular to a polymer-coated natural graphite negative electrode material, and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of relatively light weight, large storage capacity, no memory effect and the like, and is widely used. Lithium ion batteries have become a major energy source for portable electronic devices, electric Vehicles (EVs) and Energy Storage Stations (ESS) due to their high specific capacity and high energy density, as compared to conventional rechargeable batteries.
Currently, the cathode materials of lithium ion batteries mainly comprise transition metal oxides, alloys, graphite and the like. Graphite can act as a receptor for various intercalation compounds, forming binary or ternary intercalation compounds. Graphite has strong lithium intercalation capability and low cost, and is a standard negative electrode material of lithium ion batteries.
Commercial graphites are largely classified into artificial stones and natural graphites. The artificial graphite has higher coulombic efficiency and better cycle performance, but the high-temperature treatment is an essential link of the artificial graphite, which greatly increases the cost of the cathode material. Natural graphite has the advantages of low cost, high conductivity, large capacity and the like, and becomes a concern of cathode materials in recent years. Each negative electrode manufacturer distributes natural graphite separately. However, natural graphite has a large specific surface area and many exposed active sites, resulting in lower initial efficiency and poor cycle performance. The formation of an efficient and stable SEI film (solid electrolyte interfacial film) on the surface of natural graphite is an effective path for solving this fundamental problem. At present, no artificial SEI film coated natural graphite anode material is reported.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide a polymer-coated natural graphite anode material which has the advantages of high initial efficiency, high capacity and the like.
The second purpose of the invention is to provide a preparation method of the polymer-coated natural graphite anode material.
The third object of the present invention is to provide a method for applying the polymer-coated natural graphite anode material to an anode material of a lithium ion battery.
One of the purposes of the invention is realized by adopting the following technical scheme:
The polymer-coated natural graphite anode material comprises natural graphite, and a polymer coating layer and a lithium salt coating layer which are uniformly coated on the surface of the natural graphite, wherein the weight ratio of the natural graphite to the polymer in the polymer coating layer to the lithium salt in the lithium salt coating layer is 300: (1.2-5.0): (0.8-4.0).
Because the traditional lithium ion battery naturally generates an SEI film on the surface of graphite after electrolyte is decomposed in the charging process, lithium ions are consumed, leading to first effect reduction, and the SEI film naturally generated after electrolyte is decomposed mainly comprises inorganic components such as Li 2CO3, liF, li 2 O and the like, as the battery is continuously circulated, the natural graphite expands in volume, so that the naturally generated inorganic SEI film is easy to damage, and the circulation performance is reduced.
According to the natural graphite anode material, the stable artificial SEI film is formed on the surface of the natural graphite through the polymer, the polymer SEI film is firm and flexible, the problem that naturally generated inorganic SEI is unstable is avoided, the cycle performance of the graphite is improved, the specific surface of the natural graphite can be reduced through polymer coating, the active site is further reduced, the first effect is improved, a lithium salt coating layer is added on the basis of the polymer, the lithium ions consumed by adding the lithium salt can be supplemented, the first effect can be further improved, and the overall polymer coated natural graphite anode material has the advantages of high first effect, high capacity and the like.
Preferably, the weight ratio of the natural graphite to the polymer to the lithium salt is 300: (1.5-4.6): (1.1-3.4), in the matched proportion, the high first efficiency and high capacity of the integral natural graphite anode material are optimal.
Most preferably, the weight ratio of the natural graphite to the polymer to the lithium salt is 300:3.051:4.576.
Preferably, the polymer coating layer comprises a first coating agent and a second coating agent, the first coating agent is a polymer containing ether bond, the second coating agent is a polymer containing amino/imino, so that the polymer coating layer has ether bond and amino/imino, O in the ether bond and N in the amino/imino contain lone electrons and can form coordination with Li +, more ion transmission paths are provided, the first effect is further improved, and simultaneously, the ether bond and the amino/imino can have better coating effect in the graphite material through intermolecular force. Similarly, the present invention is not limited to the above-mentioned polymers, and polymers having a coordinating effect with Li + or more are included in the idea of the present invention.
Preferably, the weight ratio of the first coating agent to the second coating agent is (0.5-1.0): 1. in the matching of the adaptation, the matching effect of the first coating agent and the second coating agent is better, and the coating effect is further improved.
Further preferably, the weight ratio of the first coating agent to the second coating agent is (0.5-0.8): 1.
Most preferably, the weight ratio of the first coating agent to the second coating agent is 0.62:1.
Preferably, the first coating agent is one or more than two of polyethylene oxide, polyethylene glycol and polyethylene glycol monomethyl ether.
Preferably, the second coating agent is one or more than two of polyethylenimine, polyacrylamide and polyimide. N in polyethyleneimine, polyacrylamide and polyimide contains lone electron and can form coordination with Li +.
Most preferably, the second coating agent is polyacrylamide. The coordination effect of polyacrylamide and Li + is optimal.
Preferably, the lithium salt in the lithium salt coating layer is one or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium chloride, lithium sulfate, lithium acetate and lithium phosphate.
The second purpose of the invention is realized by adopting the following technical scheme:
the preparation method of the polymer-coated natural graphite anode material comprises the following preparation steps:
s1: dissolving a polymer in distilled water, and stirring to fully disperse the polymer to obtain a solution A;
S2: slowly adding natural graphite into the solution A, and fully stirring to obtain a suspension B;
S3: fully dissolving lithium salt in distilled water, slowly adding the solution into the suspension B, and fully stirring to uniformly disperse the lithium salt to obtain a suspension C;
s4: evaporating the suspension C in a water bath kettle at 100 ℃ to dryness to obtain viscous mixed slurry D;
S5: drying the viscous mixed slurry D in an N 2 oven at 80-100 ℃ for 6-10 h, drying most of water in an N 2 oven at 100-150 ℃ for 8-10 h after the water is evaporated to dryness, so that the polymer and the lithium salt are uniformly coated on the surface of the natural graphite, and the polymer-coated natural graphite anode material is obtained. The first drying is performed to enable the polymer to be uniformly wound on the surface of the natural graphite, and the second drying is performed to enable the polymer to be tightly coated on the surface of the natural graphite.
Preferably, the preparation method of the polymer-coated natural graphite anode material comprises the following preparation steps:
S1: dissolving the first coating agent in distilled water, and stirring for 20-40 min to fully disperse the first coating agent to obtain a solution A1;
S2: adding a second coating agent into the solution A1, stirring for 20-40 min, and fully mixing to obtain a solution A2;
s3: slowly adding natural graphite into the solution A2, and fully stirring to obtain a suspension B;
S4: fully dissolving lithium salt in distilled water, slowly adding the solution into the suspension B, and fully stirring to uniformly disperse the lithium salt to obtain a suspension C;
s5: evaporating the suspension C in a water bath kettle at 100 ℃ to dryness to obtain viscous mixed slurry D;
S6: drying the viscous suspension slurry D in an N 2 oven at 80-100 ℃ for 6-10 h, drying most of water in an N 2 oven at 100-150 ℃ for 8-10 h after the water is evaporated to dryness, so that the polymer and the lithium salt are uniformly coated on the surface of the natural graphite, and the polymer-coated natural graphite anode material is obtained. The first drying is performed to uniformly wind the first coating agent and the second coating agent on the surface of the natural graphite by intermolecular forces, and the second drying is performed to tightly coat the first coating agent and the second coating agent on the surface of the natural graphite.
The third purpose of the invention is realized by adopting the following technical scheme:
a polymer coated natural graphite negative electrode material is applied to a negative electrode material of a lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
According to the natural graphite anode material, the stable artificial SEI film is formed on the surface of the natural graphite through the polymer, the polymer SEI film is firm and flexible, the problem that naturally generated inorganic SEI is unstable is avoided, the cycle performance of the graphite is improved, the specific surface of the natural graphite can be reduced through polymer coating, the active site is further reduced, the first effect is improved, a lithium salt coating layer is added on the basis of the polymer, the lithium ions consumed by adding the lithium salt can be supplemented, the first effect can be further improved, and the overall polymer coated natural graphite anode material has the advantages of high first effect, high capacity and the like.
According to the natural graphite anode material, the first coating agent and the second coating agent are used, the first coating agent is a polymer containing ether linkage, the second coating agent is a polymer containing amino/imino, so that the polymer coating layer contains ether linkage and amino/imino, O in the ether linkage and N in the amino/imino contain lone electrons, coordination can be formed between the O and N in the amino/imino and Li +, more ion transmission paths are provided, the initial effect is further improved, and meanwhile, the ether linkage and the amino/imino can act through molecules, so that the coating effect of the ether linkage and the amino/imino in the graphite material is better.
Drawings
FIG. 1 is an optical dispersion spectrum (EDS) of O element of a natural graphite anode material of example 2 of the present invention;
Fig. 2 is an N-Element Dispersion Spectrum (EDS) diagram of the natural graphite anode material of example 2 of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific embodiments, and it should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below.
Example 1
The preparation method of the polymer-coated natural graphite anode material comprises the following preparation steps:
S1: dissolving 0.584g of polyethylene glycol in 66ml of deionized water, stirring for 20min to fully disperse the polyethylene glycol to obtain a solution A1;
S2: 0.9413g of polyacrylamide is dissolved in 400ml of water solution and stirred uniformly, then the solution A1 is added and stirred for 20min, so that the solution A2 is obtained after the solution A is fully mixed;
s3: 300g of natural graphite is slowly added into the solution A2 and stirred uniformly to obtain a suspension B.
S4: 1.117g of lithium acetate is dissolved in 50ml of deionized water, then slowly added into the suspension B, and fully stirred to uniformly disperse lithium salt, so as to obtain a suspension C;
s5: evaporating the suspension C in a water bath kettle at 100 ℃ to dryness to obtain viscous mixed slurry D;
S6: drying the viscous suspension slurry D in an N 2 oven at 90 ℃ for 8 hours, drying most of water in an N 2 oven at 140 ℃ for 10 hours after evaporating, and uniformly coating the polymer and lithium salt on the surface of the natural graphite to obtain the polymer-coated natural graphite anode material.
Example 2
The preparation method of the polymer-coated natural graphite anode material comprises the following preparation steps:
S1: dissolving 1.168 of polyethylene glycol in 66ml of deionized water, stirring for 20min to fully disperse the polyethylene glycol to obtain a solution A1;
S2: 1.883g of polyacrylamide is dissolved in 400ml of water solution and stirred uniformly, then the solution A1 is added and stirred for 20min, so that the solution A2 is obtained after the solution A is fully mixed;
s3: 300g of natural graphite is slowly added into the solution A2 and stirred uniformly to obtain a suspension B.
S4: dissolving 2.234g of lithium acetate in 50ml of deionized water, slowly adding the solution into the suspension B, and fully stirring to uniformly disperse lithium salt to obtain a suspension C;
s5: evaporating the suspension C in a water bath kettle at 100 ℃ to dryness to obtain viscous mixed slurry D;
S6: drying the viscous suspension slurry D in an N 2 oven at 90 ℃ for 8 hours, drying most of water in an N 2 oven at 140 ℃ for 10 hours after evaporating, and uniformly coating the polymer and lithium salt on the surface of the natural graphite to obtain the polymer-coated natural graphite anode material.
The O element and the N element of the natural graphite anode material obtained in this embodiment are respectively analyzed by an energy spectrometer, so as to obtain dispersion spectrum (EDS) diagrams as shown in fig. 1 and fig. 2, and it can be seen from the diagrams that the O element or the N element in the natural graphite anode material is distributed uniformly, that is, the first coating agent and the second coating agent are distributed uniformly on the surface of the natural graphite.
Example 3
The preparation method of the polymer-coated natural graphite anode material comprises the following preparation steps:
s1: 1.752g of polyethylene glycol is dissolved in 66ml of deionized water and stirred for 20min to be fully dispersed, so as to obtain solution A1;
S2: 2.824g of polyacrylamide is dissolved in 400ml of water solution and stirred uniformly, then the solution A1 is added and stirred for 20min, so that the solution A2 is obtained after the solution A is fully mixed;
s3: 300g of natural graphite is slowly added into the solution A2 and stirred uniformly to obtain a suspension B.
S4: 3.351g of lithium acetate is dissolved in 50ml of deionized water, then slowly added into the suspension B, and fully stirred to uniformly disperse lithium salt, so as to obtain a suspension C;
s5: evaporating the suspension C in a water bath kettle at 100 ℃ to dryness to obtain viscous mixed slurry D;
S6: drying the viscous suspension slurry D in an N 2 oven at 90 ℃ for 8 hours, drying most of water in an N 2 oven at 140 ℃ for 10 hours after evaporating, and uniformly coating the polymer and lithium salt on the surface of the natural graphite to obtain the polymer-coated natural graphite anode material.
Example 4
The preparation method of the polymer-coated natural graphite anode material comprises the following preparation steps:
s1: 1.168g of polyethylene glycol is dissolved in 66ml of deionized water and stirred for 20min to be fully dispersed, so as to obtain solution A1;
S2: 1.883g of polyacrylamide is dissolved in 400ml of water solution and stirred uniformly, then the solution A1 is added and stirred for 20min, so that the solution A2 is obtained after the solution A is fully mixed;
s3: 300g of natural graphite is slowly added into the solution A2 and stirred uniformly to obtain a suspension B.
S4: dissolving 2.234g of lithium hydroxide in 50ml of deionized water, slowly adding the solution into the suspension B, and fully stirring to uniformly disperse lithium salt to obtain a suspension C;
s5: evaporating the suspension C in a water bath kettle at 100 ℃ to dryness to obtain viscous mixed slurry D;
S6: drying the viscous suspension slurry D in an N 2 oven at 90 ℃ for 8 hours, drying most of water in an N 2 oven at 140 ℃ for 10 hours after evaporating, and uniformly coating the polymer and lithium salt on the surface of the natural graphite to obtain the polymer-coated natural graphite anode material.
Example 5
The preparation method of the polymer-coated natural graphite anode material comprises the following preparation steps:
S1: 1.168g of polyethylene oxide is dissolved in 66ml of deionized water and stirred for 20min to be fully dispersed, so as to obtain solution A1;
S2: 1.883g of polyacrylamide is dissolved in 400ml of water solution and stirred uniformly, then the solution A1 is added and stirred for 20min, so that the solution A2 is obtained after the solution A is fully mixed;
s3: 300g of natural graphite is slowly added into the solution A2 and stirred uniformly to obtain a suspension B.
S4: dissolving 2.234g of lithium acetate in 50ml of deionized water, slowly adding the solution into the suspension B, and fully stirring to uniformly disperse lithium salt to obtain a suspension C;
s5: evaporating the suspension C in a water bath kettle at 100 ℃ to dryness to obtain viscous mixed slurry D;
S6: drying the viscous suspension slurry D in an N 2 oven at 90 ℃ for 8 hours, drying most of water in an N 2 oven at 140 ℃ for 10 hours after evaporating, and uniformly coating the polymer and lithium salt on the surface of the natural graphite to obtain the polymer-coated natural graphite anode material.
Example 6
The preparation method of the polymer-coated natural graphite anode material comprises the following preparation steps:
S1: 1.168g of polyethylene glycol monomethyl ether is dissolved in 66ml of deionized water, and stirred for 20min to be fully dispersed, so as to obtain a solution A1;
S2: 1.883g of polyacrylamide is dissolved in 400ml of water solution and stirred uniformly, then the solution A1 is added and stirred for 20min, so that the solution A2 is obtained after the solution A is fully mixed;
s3: 300g of natural graphite is slowly added into the solution A2 and stirred uniformly to obtain a suspension B.
S4: dissolving 2.234g of lithium acetate in 50ml of deionized water, slowly adding the solution into the suspension B, and fully stirring to uniformly disperse lithium salt to obtain a suspension C;
s5: evaporating the suspension C in a water bath kettle at 100 ℃ to dryness to obtain viscous mixed slurry D;
S6: drying the viscous suspension slurry D in an N 2 oven at 90 ℃ for 8 hours, drying most of water in an N 2 oven at 140 ℃ for 10 hours after evaporating, and uniformly coating the polymer and lithium salt on the surface of the natural graphite to obtain the polymer-coated natural graphite anode material.
Example 7
The preparation method of the polymer-coated natural graphite anode material comprises the following preparation steps:
S1: 3.051g of polyethylene glycol is dissolved in 66ml of deionized water and stirred for 20min to be fully dispersed, so as to obtain solution A;
s2: 300g of natural graphite is slowly added into the solution A and stirred uniformly to obtain a suspension B.
S3: dissolving 2.234g of lithium acetate in 50ml of deionized water, slowly adding the solution into the suspension B, and fully stirring to uniformly disperse lithium salt to obtain a suspension C;
s4: evaporating the suspension C in a water bath kettle at 100 ℃ to dryness to obtain viscous mixed slurry D;
s5: drying the viscous suspension slurry D in an N 2 oven at 90 ℃ for 8 hours, drying most of water in an N 2 oven at 140 ℃ for 10 hours after evaporating, and uniformly coating the polymer and lithium salt on the surface of the natural graphite to obtain the polymer-coated natural graphite anode material.
Example 8
The preparation method of the polymer-coated natural graphite anode material comprises the following preparation steps:
S1: 3.051g of polyacrylamide is dissolved in 400ml of water solution and stirred uniformly, so that the solution A is obtained after the solution A is fully mixed;
s2: 300g of natural graphite is slowly added into the solution A and stirred uniformly to obtain a suspension B.
S3: dissolving 2.234g of lithium acetate in 50ml of deionized water, slowly adding the solution into the suspension B, and fully stirring to uniformly disperse lithium salt to obtain a suspension C;
s4: evaporating the suspension C in a water bath kettle at 100 ℃ to dryness to obtain viscous mixed slurry D;
s5: drying the viscous suspension slurry D in an N 2 oven at 90 ℃ for 8 hours, drying most of water in an N 2 oven at 140 ℃ for 10 hours after evaporating, and uniformly coating the polymer and lithium salt on the surface of the natural graphite to obtain the polymer-coated natural graphite anode material.
Comparative example 1
The preparation method of the natural graphite anode material comprises the following preparation steps:
S1: slowly adding 300g of natural graphite into deionized water, and uniformly stirring to obtain a suspension A;
s2: evaporating the suspension A in a water bath kettle at the temperature of 100 ℃ to dryness to obtain viscous mixed slurry D;
S3: and drying the viscous mixed slurry D in an N 2 oven at 90 ℃ for 8 hours, and drying the viscous mixed slurry D in an N 2 oven at 140 ℃ for 10 hours after most of water is evaporated to dryness to obtain the natural graphite anode material.
Performance testing
The materials prepared in the comparative example and the example were tested for the first specific charge capacity, the first specific discharge capacity and the first coulombic efficiency; the negative electrode materials of the above examples and comparative examples were mixed with polyvinylidene fluoride (PVdF) at a mass ratio of 9:1, and then mixed with N-methylpyrrolidone (NMP) to prepare a slurry, which was coated on a copper foil, and dried, punched and pressed to prepare a negative electrode sheet. The battery is assembled by taking a metal lithium foil as a counter electrode, taking an electrolyte of 1MLiPF 6/(PC+DMC) =1:1 and taking a polypropylene film (Celgard 2325) as a diaphragm. The charge-discharge voltage is 0-1.5V, and the charge-discharge current density is 0.2mA/cm 2. The test results are shown in the following table.
TABLE 1
| Project | Specific capacity for initial charge (mAh/g) | Specific capacity for initial discharge (mAh/g) | First coulombic efficiency (%) |
| Example 1 | 418.14 | 373.4 | 89.3 |
| Example 2 | 395.63 | 371.1 | 93.8 |
| Example 3 | 403.94 | 368.8 | 91.3 |
| Example 4 | 411.16 | 372.1 | 90.5 |
| Example 5 | 401.40 | 371.3 | 92.5 |
| Example 6 | 403.34 | 374.3 | 92.8 |
| Example 7 | 423.50 | 380.2 | 89.8 |
| Example 8 | 426.24 | 379.6 | 89.1 |
| Comparative example 1 | 430.32 | 376.1 | 87.4 |
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (5)
1. The polymer-coated natural graphite anode material is characterized by comprising natural graphite, and a polymer coating layer and a lithium salt coating layer which are uniformly coated on the surface of the natural graphite, wherein the weight ratio of the natural graphite to the polymer in the polymer coating layer to the lithium salt in the lithium salt coating layer is 300: (1.2-5.0): (0.8-4.0);
The polymer coating layer comprises a first coating agent and a second coating agent, and the weight ratio of the first coating agent to the second coating agent is (1-2): 1, the first coating agent is a polymer containing ether bond, and the second coating agent is a polymer containing amino or imino; the lithium salt in the lithium salt coating layer is one or more than two of lithium carbonate, lithium hydroxide, lithium nitrate, lithium chloride, lithium sulfate, lithium acetate and lithium phosphate;
the preparation method of the polymer-coated natural graphite anode material comprises the following preparation steps:
S1: dissolving the first coating agent in distilled water, and stirring for 20-40 min to fully disperse the first coating agent to obtain a solution A1;
S2: adding a second coating agent into the solution A1, stirring for 20-40 min, and fully mixing to obtain a solution A2;
s3: slowly adding natural graphite into the solution A2, and fully stirring to obtain a suspension B;
S4: fully dissolving lithium salt in distilled water, slowly adding the solution into the suspension B, and fully stirring to uniformly disperse the lithium salt to obtain a suspension C;
s5: evaporating the suspension C in a water bath kettle at 100 ℃ to dryness to obtain viscous mixed slurry D;
S6: drying the viscous suspension slurry D in an N 2 oven at 80-100 ℃ for 6-10 h, drying most of water in an N 2 oven at 100-150 ℃ for 8-10 h after the water is evaporated to dryness, so that the polymer and the lithium salt are uniformly coated on the surface of the natural graphite, and the polymer-coated natural graphite anode material is obtained.
2. The polymer coated natural graphite negative electrode material according to claim 1, wherein the weight ratio of natural graphite to polymer lithium salt is 300: (1.5-4.6): (1.1-3.4).
3. The polymer coated natural graphite anode material according to claim 1, wherein the first coating agent is one or more of polyethylene oxide, polyethylene glycol monomethyl ether.
4. The polymer-coated natural graphite anode material according to claim 1, wherein the second coating agent is one or more of polyethylenimine, polyacrylamide, and polyimide.
5. A polymer coated natural graphite anode material according to any one of claims 1-4 for use in anode materials for lithium ion batteries.
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