CN113184827A - Hard carbon cathode composite material and preparation method and application thereof - Google Patents
Hard carbon cathode composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113184827A CN113184827A CN202110461592.7A CN202110461592A CN113184827A CN 113184827 A CN113184827 A CN 113184827A CN 202110461592 A CN202110461592 A CN 202110461592A CN 113184827 A CN113184827 A CN 113184827A
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- China
- Prior art keywords
- hard carbon
- carbon
- lithium
- composite material
- lithiated
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 235
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 128
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 123
- 239000007833 carbon precursor Substances 0.000 claims abstract description 69
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 67
- 238000000576 coating method Methods 0.000 claims abstract description 66
- 239000011248 coating agent Substances 0.000 claims abstract description 63
- 239000011247 coating layer Substances 0.000 claims abstract description 55
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- 150000001875 compounds Chemical class 0.000 claims abstract description 22
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- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 20
- 239000007791 liquid phase Substances 0.000 claims description 19
- 239000012071 phase Substances 0.000 claims description 19
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 14
- 229930006000 Sucrose Natural products 0.000 claims description 14
- 239000005720 sucrose Substances 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 8
- 239000011280 coal tar Substances 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 239000000295 fuel oil Substances 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 239000002028 Biomass Substances 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
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- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 3
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
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- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims 1
- 229910001947 lithium oxide Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 abstract description 14
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
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Classifications
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- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
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Abstract
The invention relates to a hard carbon cathode composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: pretreating a carbon-containing raw material to prepare a hard carbon precursor; mixing the hard carbon precursor with a lithium-containing compound and a binder to prepare a solid pre-lithiated hard carbon precursor; sintering the pre-lithiated hard carbon precursor to prepare pre-lithiated hard carbon; and then carrying out carbon coating treatment on the pre-lithiated hard carbon to form a carbon coating layer on the surface of the pre-lithiated hard carbon. The lithium-carbon composite is formed by introducing exogenous lithium into the surface and bulk phase of the hard carbon, so that a certain amount of lithium is filled in the stable structure and pores of the hard carbon in advance, and the consumption of effective lithium in the battery caused by the first formation is compensated. And then, the carbon coating layer is matched to reduce the defects on the surface of the hard carbon and cover the lithium-carbon compound with higher chemical activity, so that the lithium supplementing effect can be achieved, the side reaction of the active substance and the electrolyte can be reduced, the first coulombic efficiency is synergistically improved, and the cycle life of the battery is prolonged.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a hard carbon cathode composite material and a preparation method and application thereof.
Background
Because mileage anxiety often appears in the experience of using the electric motor car in the current consumer market, the research and development of the power battery are more and more developed towards the direction of quick charging. The current quick-charging battery mainly adopts graphite as a negative electrode, realizes the quick-charging effect by reducing the surface density and the compaction density, but also can cause the energy density of the battery to be reduced, and the pure use of the graphite as the negative electrode also has the limit of multiplying power, which is a result that the battery is not accepted by the consumer market of electric automobiles. If the current cathode material is changed from the pure graphite into the hard carbon material or the composite material formed by compounding the hard carbon material and the graphite, the multiplying power performance and the energy density of the battery can be further improved, and the energy density of the battery can be improved on the premise of ensuring the multiplying power charging of the battery, so that the electric automobile has the quick charging performance and the long endurance capacity.
The conversion of the negative electrode material from graphite to a hard carbon material can improve the multiplying power performance of the battery to a great extent and improve the energy density of the power battery, so that the cruising anxiety of the electric vehicle is greatly relieved on the charging speed and the endurance mileage. However, the hard carbon has an intrinsic amorphous structure and more pores, so that it consumes a large amount of active lithium during the first lithium intercalation, resulting in a lower first coulombic efficiency (also called first efficiency or first effect), so that it has many difficulties in application to power batteries. How to improve the first effect of such materials becomes the focus of research in the industry and academia at present.
Prelithiation is the introduction of exogenous lithium into the battery system in a suitable manner and form to ameliorate the first coulombic efficiency reduction due to the consumption of active lithium by the negative electrode material during charging and discharging. Currently, the prelithiation mainly comprises positive prelithiation and negative prelithiation, wherein the negative prelithiation is researched more and the technology is relatively mature. The negative electrode pre-lithiation is divided into direct addition of exogenous lithium, active additive pre-lithiation, electrochemical pre-lithiation and chemical pre-lithiation according to a pre-lithiation mode, and is divided into material layer pre-lithiation, pole piece pre-lithiation and battery pre-lithiation from the pre-lithiation layer. The current prelithiation technology mainly adopts prelithiation of a pole piece layer, but the prelithiation process of the pole piece layer needs to add a prelithiation process step and corresponding equipment and environmental space, which can greatly increase the time cost, equipment investment cost and plant reconstruction cost of lithium battery manufacture, and is not beneficial to popularization and application of the prelithiation technology.
Although the prelithiation is an effective means for improving the first coulombic efficiency of the negative electrode material, the prelithiation is generally applied to improving the first coulombic efficiency of the silicon-based negative electrode, and the research or application for improving the first coulombic efficiency of the hard carbon material through the prelithiation is less.
After being consulted, the Chinese patent CN 110148734A discloses a pre-lithiated hard carbon and a preparation method thereof, and the steps comprise: (1) pretreating a carbon-containing raw material to obtain a hard carbon precursor; (2) carrying out pre-lithiation treatment on the hard carbon precursor so as to obtain a solid pre-lithiated hard carbon precursor with the surface coated with a lithium-containing substance; (3) coating the pre-lithiated hard carbon precursor with pitch; (4) and (4) carbonizing the coated pre-lithiated hard carbon precursor obtained in the step (3) in an inert atmosphere, and crushing, screening and demagnetizing to obtain the hard carbon negative electrode material. The patent adopts a liquid phase method to carry out pre-lithiation on a hard carbon precursor, specifically, lithium fluoride generated by lithium acetate or lithium oxalate and ammonium fluoride in a solution is attached to the surface of hard carbon to realize pre-lithiation, only a small part of lithium fluoride in a system is attached to the surface of hard carbon through physical adsorption, so that great waste and pollution are generated, and the attachment amount of the lithium fluoride to the surface of the hard carbon is difficult to control, so that the pre-lithiation degree is inconsistent between batches, and the properties of the material are inconsistent.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a hard carbon negative electrode composite material capable of remarkably improving the first coulombic efficiency of a lithium secondary battery.
The technical scheme is as follows:
a preparation method of a hard carbon negative electrode composite material comprises the following steps:
pretreating a carbon-containing raw material to prepare a hard carbon precursor;
mixing the hard carbon precursor with a lithium-containing compound and a binder to prepare a solid pre-lithiated hard carbon precursor;
sintering the pre-lithiated hard carbon precursor to prepare pre-lithiated hard carbon;
and carrying out carbon coating treatment on the pre-lithiated hard carbon to form a carbon coating layer on the surface of the pre-lithiated hard carbon.
In one embodiment, the hard carbon precursor, the lithium-containing compound and the binder are mixed mechanically at a temperature of 150 to 250 ℃ and a rotation speed of 10 to 200 rpm.
In one embodiment, the sintering treatment temperature is 700-1000 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 1-6 h.
In one embodiment, the carbonaceous feedstock is selected from a mixture of one or more of a polymeric material, a coal-based material, and a biomass-based material. The polymer material is selected from one or more of phenolic resin, polytetrafluoroethylene, polyacrylic acid, epoxy resin, furan resin, polyfurfuryl alcohol, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyaniline and polyimide. The coal material is selected from one or more of anthracite, bituminous coal, lignite and coal tar. The biomass material is selected from sucrose, glucose and derivatives thereof, or materials containing fiber substances; such as rice, sugarcane, rape, cotton, barley, wheat, corn, reed, sisal, bamboo, peanut, seaweed, towel gourd, pumpkin, jujube wood, oak, peach wood, coconut shell, sweet potato, cassava, beet, potato, celery, soybean, poplar, paulownia wood, locust tree, banana tree, water hyacinth and machine-made wood, and extracts (such as sucrose, glucose and starch) obtained by certain extraction and transformation means.
In one embodiment, the lithium-containing compound is selected from a mixture of one or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium oxalate, lithium chloride, lithium sulfide, lithium fluoride, lithium acetate, lithium oxy-hexafluorophosphate and lithium tetrafluoroborate.
In one embodiment, the binder is selected from one or more of asphalt, heavy oil, coal tar, polytetrafluoroethylene, polyvinylidene fluoride and hydrocarbons with the carbon number of 6-14.
In one embodiment, the mass ratio of the hard carbon precursor, the lithium-containing compound and the binder is (72-94): (5-23): 1-5).
In one embodiment, the carbon coating is performed by a method selected from liquid phase coating or gas phase coating.
In one embodiment, the carbon coating is a liquid phase coating, and the liquid phase coated carbon source is selected from a mixture of one or more of coal tar, paraffin, liquid hydrocarbons, heavy oil and derivatives thereof, sucrose, glucose and polyvinylidene fluoride.
In one embodiment, the carbon coating is liquid phase coating, and after the liquid phase coating step, carbonization treatment is further performed, wherein the carbonization temperature is 700-1200 ℃, and the carbonization time is 1-5 h.
In one embodiment, the gas phase coating is a chemical gas phase coating or a physical gas phase coating.
In one embodiment, the chemical vapor-coated carbon source is selected from a mixed gas of one or more of propyne, propylene, methane, ethane, propane, ethylene, acetylene, benzene, toluene, xylene, styrene, and ethylbenzene.
In one embodiment, the temperature of the chemical vapor phase coating is 700-1000 ℃, and the time is 0.5-6 h.
In one embodiment, the carbon coating layer accounts for 0.1-5 wt% of the hard carbon negative electrode composite material, the median particle size (D50) of the hard carbon precursor is 5-30 μm, and the thickness of the carbon coating layer is 5-1000 nm.
In one embodiment, the pre-processing comprises: and (3) carrying out crushing treatment and heat treatment on the carbon-containing raw material.
In one embodiment, the heat treatment is carried out in an oxygen-containing atmosphere at a temperature of 150 ℃ to 300 ℃ for 1h to 5 h.
The invention also provides a hard carbon negative electrode composite material prepared by the preparation method of the hard carbon negative electrode composite material.
The invention also provides an application of the hard carbon negative electrode composite material. The technical scheme is as follows:
a lithium secondary battery comprising the hard carbon anode composite of any of the embodiments.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the hard carbon cathode composite material provided by the invention comprises the steps of pretreating a carbon-containing raw material to prepare a hard carbon precursor; mixing the hard carbon precursor with a lithium-containing compound and a binder to prepare a pre-lithiated hard carbon precursor; sintering the pre-lithiated hard carbon precursor to prepare pre-lithiated hard carbon; and a step of forming a carbon coating layer on the surface of the pre-lithiated hard carbon by performing carbon coating treatment on the pre-lithiated hard carbon.
By pretreating the carbon-containing raw material, impurities in the carbon-containing raw material can be removed, which is beneficial to improving the quality of the hard carbon precursor. In the step of mixing the hard carbon precursor, the lithium-containing compound and the binder, the hard carbon precursor and the lithium-containing compound are more firmly bound together under the action of the binder, so that a lithium source is fully attached to the surface of the hard carbon precursor, the rapid infiltration of lithium during subsequent sintering treatment is facilitated, and the integrity of the hard carbon precursor can be ensured; compared with solid-liquid mixing, the solid-solid mixing can avoid huge cost increase and environmental pollution caused by repeated cleaning in a liquid phase method; on the other hand, the addition amount of the lithium-containing compound can be accurately controlled, the pre-lithiation degree of the hard carbon material can be better controlled, and the performance consistency of the pre-lithiation hard carbon composite material among batches can be ensured. Sintering the uniformly mixed pre-lithiated hard carbon precursor, so that on one hand, the content of heteroatoms in the hard carbon can be reduced to form a more stable amorphous structure, and on the other hand, lithium and carbon can be promoted to form a lithium-carbon compound to complete pre-lithiation of a material layer; the generated lithium-carbon composite can be consumed when an SEI film is formed on the interface of the negative electrode during the formation of the battery, and can also be pre-filled in a hard carbon pore structure or form dangling bond lithium storage, so that lithium ions which are extracted from an electrolyte and a positive electrode material can be prevented from being consumed when the SEI film is formed, the storage capacity of active lithium in a system can be increased, and the capacity and the first coulombic efficiency of the battery can be improved. After the pre-lithiation is finished, the pre-lithiation hard carbon is subjected to carbon coating treatment, and a carbon coating layer is formed on the surface of the pre-lithiation hard carbon, so that the defects on the surface of the pre-lithiation hard carbon can be reduced, O-containing and H-containing groups on the surface of the hard carbon are shielded, the specific surface area of the hard carbon is reduced, the layer stripping of the hard carbon caused by irreversible loss and the co-insertion of solvent molecules due to excessive SEI (solid electrolyte interphase) film formation is reduced, the first coulombic efficiency is further improved, and the cycle life of the battery is prolonged; most importantly, the lithium-carbon compound with higher chemical activity is covered by the carbon coating layer, and the lithium-carbon compound is physically separated from the electrolyte, so that the lithium supplementing effect can be achieved, the side reaction of the active substance and the electrolyte can be reduced, the first coulombic efficiency can be synergistically improved, and the cycle life of the battery can be prolonged. In addition, the method is simple to operate, is suitable for industrial production, and has wide application prospect.
The hard carbon cathode composite material prepared by the preparation method of the hard carbon cathode composite material provided by the invention is a material (micron-sized particles) with a core-shell structure, the interior of the hard carbon composite material is a pre-lithiated hard carbon core, the outer layer of the hard carbon composite material is a carbon coating layer, and the surface and the bulk phase of the hard carbon composite material both contain exogenous lithium to form a lithium-carbon composite, so that the consumption of effective lithium in a battery caused by first formation can be compensated.
The hard carbon negative electrode composite material provided by the invention is applied to the negative electrode of a lithium secondary battery, so that the consumption of electrolyte and effective lithium in the battery can be effectively reduced, the electrolyte injection amount required by the production of the lithium ion battery and the generation of gas generated during the working of a lithium battery product are reduced, the production process flow and the formation flow of the lithium ion battery are simplified, the problem of unstable SEI (solid electrolyte interphase) in the conventional lithium battery is solved, the first coulombic efficiency, the cycle life and the rate capability of the battery negative electrode are improved while the negative electrode is ensured to exert high specific capacity, and an optional material is provided for the commercialization of a high-rate and high-energy density battery.
Tests show that the charge-discharge reversible capacity of the battery can reach 506mAh/g, the first coulombic efficiency can reach 92.39%, and the capacity can be kept at about 95.4% after 100 weeks of circulation.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, as another element may be added, unless an explicit limitation is used, such as "only," "consisting of … …," etc.
Unless mentioned to the contrary, terms in the singular may include the plural and are not to be construed as being one in number.
The invention provides a preparation method of a hard carbon negative electrode material capable of remarkably improving the first coulombic efficiency and the cycle life of a lithium ion secondary battery.
The technical scheme is as follows:
a preparation method of a hard carbon negative electrode composite material comprises the following steps:
pretreating a carbon-containing raw material to prepare a hard carbon precursor;
mixing the hard carbon precursor with a lithium-containing compound and a binder to prepare a solid pre-lithiated hard carbon precursor;
sintering the pre-lithiated hard carbon precursor to prepare pre-lithiated hard carbon;
and carrying out carbon coating treatment on the pre-lithiated hard carbon to form a carbon coating layer on the surface of the pre-lithiated hard carbon.
The preparation method of the hard carbon negative electrode composite material provided by one embodiment of the invention comprises the following steps:
s100: pretreating carbon-containing raw material to prepare hard carbon precursor
In this step, impurities in the carbon-containing raw material can be removed by pretreating the carbon-containing raw material, which is advantageous for improving the quality of the hard carbon precursor.
Preferably, the pre-treatment comprises: screening, washing and drying processes to remove a portion of the impurities, it is understood that not every carbonaceous material need be subjected to screening, washing, drying and pulverizing processes, and that for carbonaceous materials that are inherently high in purity and/or small in particle size, the step S100 may be omitted directly or at least one of the screening, washing, drying and pulverizing processes may be performed. And then crushing the hard carbon precursor (the median particle size of the hard carbon precursor after the crushing is 10-100 microns), reducing the particle size of the carbon-containing raw material through the crushing, further increasing the specific surface area of the carbon-containing raw material, and facilitating the next step of completing the pre-oxidation process of the carbon-containing raw material.
The crushed carbon-containing raw material is subjected to heat treatment (preoxidation treatment), so that the relatively low conductivity and the degree of cross-linking between carbon layers and few lithium ion storage sites of the hard carbon material obtained by a direct carbonization mode can be avoided, and the poor electrochemical performance is caused. By adding an air pre-oxidation process before carbonization, groups beneficial to electrochemical lithium storage can be introduced, the cross-linking degree of the material is enhanced, and the conductivity of the material is improved, so that the electrochemical performance of the hard carbon material is improved. More preferably, the heat treatment is carried out in air or oxygen gas atmosphere, the temperature is 150-300 ℃, and the time is 5-24 h.
The carbon-containing raw materials selected by the invention are wide in source and easy to obtain, especially coal and biomass materials, are low in price and high in carbon content, and can greatly reduce the production cost of hard carbon materials.
In one embodiment, the carbonaceous feedstock is selected from a mixture of one or more of a polymeric material, a coal-based material, and a biomass-based material. Wherein the polymer material is selected from one or more of phenolic resin, polytetrafluoroethylene, polyacrylic acid, epoxy resin, furan resin, polyfurfuryl alcohol, polytetrafluropropyl, polyvinylidene fluoride, polyvinyl chloride, polyaniline and polyimide. The coal-based material may be selected from a mixture of one or more of anthracite, bituminous coal, lignite and coal tar. The biomass material can be selected from sucrose, glucose and derivatives thereof, or materials containing sucrose, glucose and derivatives thereof, and fiber substances; such as rice, sugarcane, rape, cotton, barley (including barley straw, barley grain and barley products), wheat (including wheat straw, wheat grain and wheat products), corn (including corn stalk and corn cob), reed, sisal, bamboo, peanut, seaweed, towel gourd, pumpkin, jujube wood, oak, peach wood, coconut shell, sweet potato, cassava, potato, celery, soybean, poplar, tung wood, locust tree, banana tree, water hyacinth and machine-made wood, and extracts (such as sucrose, glucose and starch) obtained by certain extraction and transformation means.
S200: mixing the hard carbon precursor with a lithium-containing compound and a binder to prepare a solid pre-lithiated hard carbon precursor
The hard carbon precursor and the lithium-containing compound are more firmly bonded together under the action of the binder, so that a lithium source is fully attached to the surface of the hard carbon precursor, the rapid penetration of lithium during subsequent sintering treatment is facilitated, and the integrity of the hard carbon precursor can be ensured; compared with solid-liquid mixing, the solid-solid mixing can avoid huge cost increase and environmental pollution caused by repeated cleaning in a liquid phase method; on the other hand, the addition amount of the lithium-containing compound can be accurately controlled, the pre-lithiation degree of the hard carbon material can be better controlled, and the performance consistency of the pre-lithiation hard carbon composite material among batches can be ensured.
In one embodiment, the lithium-containing compound is selected from a mixture of one or more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium oxalate, lithium chloride, lithium sulfide, lithium fluoride, lithium acetate, lithium oxy-hexafluorophosphate and lithium tetrafluoroborate.
In one embodiment, the binder is selected from one or more of asphalt, heavy oil, coal tar, polytetrafluoroethylene, polyvinylidene fluoride and hydrocarbons with the carbon number of 6-14.
In one embodiment, the mass ratio of the hard carbon precursor, the lithium-containing compound and the binder is (72-94): (5-23): 1-5).
Further, if the mixing system is kept at a certain temperature during the process of mixing the hard carbon precursor, the lithium-containing compound and the binder, the binder can be more easily softened during mixing, so that the binder is more uniformly distributed on the surface of the hard carbon, and the lithium compound is uniformly adhered to the surface of the hard carbon. Preferably, the temperature of mixing is 150 ℃ to 250 ℃.
Further, if the hard carbon precursor, the lithium-containing compound and the binder are mixed in a mechanical mixing manner, the hard carbon precursor and the lithium-containing compound can be fully contacted and fully and uniformly mixed in a short time, and the uniformity of the pre-lithiation degree between the pre-lithiated hard carbon precursors is ensured. Preferably, the mechanical mixing is ball milling mixing or mechanical fusion, and the rotating speed is 10 rpm-200 rpm.
S300: sintering the pre-lithiated hard carbon precursor to prepare the pre-lithiated hard carbon
And sintering the uniformly mixed pre-lithiated hard carbon precursor, so that the content of heteroatoms in the hard carbon can be reduced to form a more stable amorphous structure, and lithium and carbon can be promoted to form a lithium-carbon compound to complete pre-lithiation of a material layer. The generated lithium-carbon composite can be consumed when an SEI film is formed on the interface of the negative electrode during the formation of the battery, and can also be filled in a hard carbon pore structure in advance or form dangling bond lithium storage, so that lithium ions which are extracted from an electrolyte and a positive electrode material can be prevented from being consumed when the SEI film is formed, the storage capacity of active lithium in a system can be increased, and the capacity and the first coulombic efficiency of the battery can be improved.
Further, in order to optimize the structure of the hard carbon to improve the lithium storage capacity and rate capability of the hard carbon, optimization may be performed in terms of a temperature rise rate, a sintering temperature, and a holding time. In one preferable embodiment, the sintering treatment temperature is 700-1000 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 1-6 h.
Furthermore, in order to further coat the pre-lithiated hard carbon, facilitate the exertion of lithium storage performance of the hard carbon and improve the rate capability of the material, the pre-lithiated hard carbon is also subjected to grinding treatment, and the median particle size of the ground pre-lithiated hard carbon is 5-30 μm.
S400: sintering the pre-lithiated hard carbon precursor to prepare the pre-lithiated hard carbon
After the pre-lithiation is finished, the pre-lithiation hard carbon is subjected to carbon coating treatment, and a carbon coating layer is formed on the surface of the pre-lithiation hard carbon, so that the defects on the surface of the pre-lithiation hard carbon can be reduced, O-containing and H-containing groups on the surface of the hard carbon are shielded, the specific surface area of the hard carbon is reduced, the layer stripping of the hard carbon caused by irreversible loss and the co-insertion of solvent molecules due to excessive SEI (solid electrolyte interphase) film formation is reduced, the first coulombic efficiency is further improved, and the cycle life of the battery is prolonged; most importantly, the lithium-carbon compound with higher chemical activity is covered by the carbon coating layer, and the lithium-carbon compound is physically separated from the electrolyte, so that the lithium supplementing effect can be achieved, and the side reaction of the active substance and the electrolyte can be reduced.
In one embodiment, the carbon coating layer accounts for 0.1-5% of the hard carbon negative electrode composite material by weight, and the thickness of the carbon coating layer is 5-1000 nm.
In one embodiment, the hard carbon negative electrode composite material has a particle size of 1 μm to 30 μm.
In one embodiment, the carbon coating treatment is selected from liquid phase coating or gas phase coating, and the gas phase coating is chemical vapor Coating (CVD) or physical vapor coating (PVD), preferably chemical vapor Coating (CVD). The purpose of carbon coating can be achieved through liquid phase coating or gas phase coating, the liquid phase coating is low in cost, the coating uniformity and the integrity of the coating layer are low, the gas phase coating can more accurately control the thickness of the coating layer, the integrity of the coating layer can also be guaranteed to be high, and the gas phase coating is low in efficiency and high in cost. The temperature, the coating time and the carbon source of the coating all influence the formation of the coating layer, and finally influence the first efficiency, the rate capability and the gram capacity of the battery, and the coated material is the hard carbon cathode composite material. Preferably, after the step of liquid phase coating, carbonization treatment is further carried out, wherein the carbonization temperature is 700-1200 ℃, and the carbonization time is 1-5 h. Preferably, the temperature of the chemical vapor coating is 700-1000 ℃, and the time of the chemical vapor coating is 0.5-6 h.
Further, a suitable carbon coating layer may also improve the electron conductivity and ion conductivity of the hard carbon, thereby improving the rate capability of the negative electrode.
In one embodiment, the liquid phase coated carbon source is selected from a mixture of one or more of coal tar, paraffin, liquid hydrocarbons, heavy oil and its derivatives (preferably pitch), sucrose, glucose, and polyvinylidene fluoride.
In one embodiment, the gas-phase-coated carbon source is selected from a mixed gas of one or more of propyne, propylene, methane, ethane, propane, ethylene, acetylene, benzene, toluene, xylene, styrene, and ethylbenzene.
The invention also provides a hard carbon negative electrode composite material prepared by the preparation method of the hard carbon negative electrode composite material, which is a material (mostly micron-sized particles) with a core-shell structure, wherein the interior of the material is a pre-lithiated hard carbon core, and the outer layer is a carbon coating layer. According to the invention, the introduction of exogenous lithium is completed at the material end, and exogenous lithium is introduced into the surface and bulk phase of the hard carbon to form a lithium-carbon composite, so that a certain amount of lithium is filled in the stable structure and pores of the hard carbon in advance, and the consumption of effective lithium in the battery caused by the first formation is compensated.
The invention also provides an application of the hard carbon negative electrode composite material. The technical scheme is as follows:
a lithium secondary battery having an anode comprising the hard carbon anode composite of any of the embodiments.
The present invention will be further described with reference to specific examples.
Example 1
The embodiment provides a hard carbon negative electrode composite material and a preparation method thereof.
(1) Crushing 100g of sucrose by using a ball mill to obtain carbon-containing raw material particles with the diameter D50 being 30 mu m;
(2) carrying out heat treatment in the air atmosphere, wherein the temperature of the heat treatment is 200 ℃, and the time is 10 hours, so as to prepare a hard carbon precursor;
(3) mixing 9.0g of the hard carbon precursor obtained in the step (2) with 0.9g of lithium carbonate and 0.1g of asphalt, and fusing in a mechanical fusion machine at 230 ℃ and at the rotating speed of 50rpm to obtain a pre-lithiated hard carbon precursor with the surface coated with a lithium compound;
(4) heating to 850 ℃ at a heating rate of 5 ℃/min under an inert atmosphere, preserving heat for 3h, sintering the pre-lithiated hard carbon precursor to prepare pre-lithiated hard carbon, cooling to normal temperature, and crushing the pre-lithiated hard carbon to obtain the pre-lithiated hard carbon with the D50 of 16 mu m;
(5) and (2) carrying out carbon coating on the pre-lithiated hard carbon by using acetylene as a carbon source and adopting a chemical vapor deposition process at the temperature of 950 ℃, wherein the carbon coating duration is 3h, so as to obtain a hard carbon cathode composite material finished product, wherein the particle size of the obtained hard carbon cathode composite material finished product is D50-16.2 mu m, the thickness of the carbon coating layer is 200nm, and the weight ratio of the carbon coating layer is 3.5%.
Example 2
This example provides a hard carbon negative electrode composite material and a method for preparing the same, which are different from example 1 in that a carbon-containing raw material is replaced with coconut shells from sucrose in step (1), and the coconut shells are further subjected to a pulverization treatment, wherein the pulverized material D50 is 100 μm. The particle size of the final hard carbon negative electrode composite material product is D50 ═ 16.2 mu m, the thickness of the carbon coating layer is 200nm, and the weight of the carbon coating layer accounts for 3.5%.
Example 3
This example provides a hard carbon negative electrode composite material and a method for preparing the same, which is different from example 1 in that the temperature of the heat treatment in step (2) is 300 ℃. The particle size of the final hard carbon negative electrode composite material product is D50 ═ 16.2 mu m, the thickness of the carbon coating layer is 200nm, and the weight of the carbon coating layer accounts for 3.5%.
Example 4
This example provides a hard carbon negative electrode composite material and a method for preparing the same, which is different from example 1 in that a hard carbon precursor having a D50 of 10 μm is obtained in step (1). The particle size of the final hard carbon negative electrode composite material product is D50 ═ 10.4 mu m, the thickness of the carbon coating layer is 400nm, and the weight of the carbon coating layer accounts for 4.9%.
Example 5
This example provides a hard carbon negative electrode composite material and a method for preparing the same, which is different from example 1 in that a hard carbon precursor having a D50 of 30 μm is obtained in step (1). The particle size of the final hard carbon negative electrode composite material product is D50 ═ 30.2 mu m, the thickness of the carbon coating layer is 200nm, and the weight of the carbon coating layer accounts for 1.5%.
Example 6
This example provides a hard carbon anode composite material and a method for preparing the same, which is different from example 1 in that 9.1g of a hard carbon precursor was mixed with 0.7g of lithium carbonate and 0.2g of pitch in step (3). The particle size of the final hard carbon negative electrode composite material is D50 ═ 8 mu m, the thickness of the carbon coating layer is 100nm, and the weight of the carbon coating layer accounts for 1.8%.
Example 7
This example provides a hard carbon negative electrode composite material and a method for preparing the same, which is different from example 1 in that 9.1g of a hard carbon precursor is mixed with 0.7g of lithium hydroxide and 0.2g of pitch in step (3). The particle size of the final hard carbon negative electrode composite material product is D50 ═ 10 mu m, the thickness of the carbon coating layer is 5nm, and the weight of the carbon coating layer accounts for 0.9%.
Example 8
The present embodiment provides a hard carbon negative electrode composite material and a preparation method thereof, which are different from those in embodiment 1 in that in step (3), a hard carbon precursor is fused with lithium carbonate and pitch in a ball mill at 180 ℃ to obtain a pre-lithiated hard carbon precursor with a surface coated with a lithium compound. The particle size of the final hard carbon cathode composite material finished product is D50 ═ 14 mu m, the thickness of the carbon coating layer is 150nm, and the weight of the carbon coating layer accounts for 2.1%.
Example 9
The present embodiment provides a hard carbon negative electrode composite material and a preparation method thereof, which are different from example 1 in that in step (4), the temperature is raised to 950 ℃ at a heating rate of 10 ℃/min under an inert atmosphere, the temperature is maintained for 2 hours, pre-lithiated hard carbon with a D50 of 12 μm is obtained after pulverization, the particle size of the final hard carbon negative electrode composite material is D50 of 12.1 μm, the thickness of a carbon coating layer is 100nm, and the weight of the carbon coating layer accounts for 2.4%.
Example 10
The present embodiment provides a hard carbon negative electrode composite material and a preparation method thereof, which are different from example 1 in that in step (4), the temperature is raised to 750 ℃ at a heating rate of 3 ℃/min under an inert atmosphere, the temperature is maintained for 6 hours, and pre-lithiated hard carbon with a D50 of 25 μm is obtained after pulverization, the particle size of the final hard carbon negative electrode composite material is D50 of 25.4 μm, the thickness of a carbon coating layer is 400nm, and the weight ratio of the carbon coating layer is 2.4%.
Example 11
The present embodiment provides a hard carbon negative electrode composite material and a preparation method thereof, which are different from example 1 in that in step (5), toluene is used as a carbon source, carbon coating is performed on pre-lithiated hard carbon by using a chemical vapor deposition process at a temperature of 900 ℃, the carbon coating duration is 1h, a hard carbon negative electrode composite material finished product is obtained, the particle size of the finally obtained hard carbon negative electrode composite material finished product is D50 ═ 16.1 μm, the thickness of the carbon coating layer is 100nm, and the weight proportion of the carbon coating layer is 1.8%.
Example 12
The present embodiment provides a hard carbon negative electrode composite material and a preparation method thereof, which are different from embodiment 1 in that in step (5), heavy oil is used as a carbon source, a liquid phase coating process is used to perform carbon coating on pre-lithiated hard carbon, the pre-lithiated hard carbon is carbonized at 1100 ℃ for 4 hours, a hard carbon negative electrode composite material finished product is obtained, the particle size of the finally obtained hard carbon negative electrode composite material finished product is D50 ═ 16.3 μm, the thickness of the carbon coating layer is 300nm, and the weight ratio of the carbon coating layer is 5.0%.
Example 13
The embodiment provides a hard carbon negative electrode composite material and a preparation method thereof, and the difference from embodiment 1 is that in step (5), sucrose is used as a carbon source, a liquid phase coating process is adopted to perform carbon coating on pre-lithiated hard carbon, carbonization is performed at 900 ℃ for 2 hours, and a hard carbon negative electrode composite material finished product is obtained, wherein the particle size of the obtained hard carbon negative electrode composite material finished product is D50 ═ 16.2 μm, the thickness of the carbon coating layer is 150nm, and the weight ratio of the carbon coating layer is 2.5%.
Example 14
The embodiment provides a hard carbon negative electrode composite material and a preparation method thereof, and the difference from embodiment 1 is that in step (5), dodecane is used as a carbon source, a liquid phase coating process is adopted to perform carbon coating on pre-lithiated hard carbon, carbonization is performed at 1000 ℃ for 3 hours, and a hard carbon negative electrode composite material finished product is obtained, wherein the particle size of the obtained hard carbon negative electrode composite material finished product is D50-16.2 μm, the thickness of a carbon coating layer is 240nm, and the weight ratio of the carbon coating layer is 4.2%.
Comparative example 1
(1) Crushing 100g of sucrose by using a ball mill to obtain carbon-containing raw material particles with the diameter D50 being 30 mu m;
(2) carrying out heat treatment in the air atmosphere, wherein the temperature of the heat treatment is 200 ℃, and the time is 10 hours, so as to prepare a hard carbon precursor;
(3) heating to 850 ℃ at the heating rate of 5 ℃/min under the inert atmosphere, and preserving heat for 3h to obtain hard carbon;
(4) taking acetylene as a carbon source, and carrying out carbon coating on hard carbon at the temperature of 950 ℃ by adopting a chemical vapor deposition process, wherein the carbon coating duration is 3h, so as to obtain the finished hard carbon cathode composite material, the particle size of the obtained hard carbon cathode composite material is D50-15.2 mu m, the thickness of the carbon coating layer is 200nm, and the weight of the carbon coating layer accounts for 3.7%.
Comparative example 2
(1) Crushing 100g of sucrose by using a ball mill to obtain carbon-containing source material particles with the D50 being 30 mu m;
(2) carrying out heat treatment in the air atmosphere, wherein the temperature of the heat treatment is 200 ℃, and the time is 10 hours, so as to prepare a hard carbon precursor;
(3) mixing 9.0g of hard carbon precursor with 0.9g of lithium carbonate and 0.1g of asphalt, and fusing in a mechanical fusing machine at 230 ℃ to obtain a pre-lithiated hard carbon precursor with the surface coated with a lithium compound;
(4) heating to 850 ℃ at the heating rate of 5 ℃/min under the inert atmosphere, preserving heat for 3h, and crushing to obtain the pre-lithiated hard carbon with the D50 being 17 mu m.
Comparative example 3
(1) Crushing 100g of sucrose by using a ball mill to obtain carbon-containing source material particles with the D50 being 30 mu m;
(2) carrying out heat treatment in the air atmosphere, wherein the temperature of the heat treatment is 200 ℃, and the time is 10 hours, so as to prepare a hard carbon precursor;
(3) heating to 850 ℃ at the heating rate of 5 ℃/min under the inert atmosphere, and preserving heat for 3h to obtain the hard carbon.
Testing
Homogenizing and coating the hard carbon negative electrode composite material obtained in the examples 1-14 and the comparative example 1, the pre-lithiated hard carbon material obtained in the comparative example 2 and the hard carbon material obtained in the comparative example 3 to obtain a negative electrode sheet, and assembling a negative electrode, a positive electrode, a diaphragm and electrolyte into a button lithium secondary battery. And (3) carrying out electrochemical performance detection on the button cell, and detecting the charge-discharge reversible capacity, the first coulombic efficiency and the capacity retention rate of the battery after 100 cycles.
1. Trial production of the battery:
1) preparation of negative plate
The hard carbon negative electrode composite materials obtained in examples 1 to 14 and comparative example 1, the pre-lithiated hard carbon material obtained in comparative example 2, the hard carbon material obtained in comparative example 3, conductive carbon black (SP) serving as a conductive agent and a binder (CMC-SBR,1/1wt) are mixed according to a mass ratio of 95:2:3, a proper amount of deionized water is added to obtain negative electrode active slurry, the negative electrode active slurry is coated on two functional surfaces of a Cu foil, and a negative electrode sheet is obtained after drying. The surface density of the negative plate is 10mg/cm2The compacted density is 1.5g/cm3。
2) Preparation of Positive plate
Setting the N/P ratio to 1.1 according to the specific capacity and the surface density of the negative electrode, and adding Li (Ni)0.5Co0.2Mn0.3)O2Mixing the positive electrode active material, SP and PVDF binder at a mass ratio of 94:3:3, adding N-methylpyrrolidone (NMP) to obtain positive electrode active slurry, and coating the positive electrode active slurry on the functional surface of the carbon-coated Al foil to obtain a positive electrode sheet.
3) Electricity buckling preparation method for lithium ion battery
Cutting the negative electrode piece obtained in the step 1) into a circular piece with the diameter of 14mm, and assembling into a 2032 type buckling battery.
4) Preparation of lithium ion soft package full battery
Assembling the negative plate obtained in the step 1), the positive plate obtained in the step 2) and the diaphragm into a battery, and injecting electrolyte to prepare the soft package full battery.
2. Electrochemical testing:
1) specific discharge capacity: discharging the button cell to 0.005V at the current of 0.1C, and calculating the specific discharge capacity according to the discharge capacity and the active material loading capacity;
2) charging specific capacity: charging the button cell which is discharged for the first time to 2.0V by 0.1C current, and calculating the discharge specific capacity according to the discharge capacity and the active material loading capacity;
3) capacity retention ratio of full cell at 100 weeks: and (3) carrying out cyclic charge and discharge according to a charge and discharge system of 0.5C/1C, wherein the ratio of the discharge capacity at the 100 th week to the first discharge capacity is the capacity retention rate.
Specific discharge capacity, specific charge capacity, first coulombic efficiency at charging, capacity retention ratio after full 100 weeks of the lithium secondary batteries of examples 1 to 14 and comparative examples 1 to 3 are shown in table 1.
TABLE 1
As can be seen from table 1, the first coulombic efficiency and the cycle performance of the lithium ion batteries of examples 1 to 14 are significantly better than those of comparative examples 1 to 3 when the hard carbon is subjected to the pre-lithiation treatment and the carbon coating treatment by the method of the present invention.
In comparative example 1, since the hard carbon material was not subjected to the pre-lithiation treatment, the lithium supplementation of the hard carbon material was not performed, which affects the first coulombic efficiency and cycle life of the battery.
In comparative example 2, the carbon coating layer was omitted and the chemically highly active lithium-carbon composite could not be covered, and the active material (lithium-carbon composite) was subject to side reaction with the electrolyte, thereby affecting the first coulombic efficiency and cycle life of the battery.
In comparative example 3, omitting both the prelithiation treatment and the carbon coating layer affected the first coulombic efficiency and cycle life of the cell.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the hard carbon negative electrode composite material is characterized by comprising the following steps:
pretreating a carbon-containing raw material to prepare a hard carbon precursor;
mixing the hard carbon precursor with a lithium-containing compound and a binder to prepare a solid pre-lithiated hard carbon precursor;
sintering the pre-lithiated hard carbon precursor to prepare pre-lithiated hard carbon;
and carrying out carbon coating treatment on the pre-lithiated hard carbon to form a carbon coating layer on the surface of the pre-lithiated hard carbon.
2. The method for preparing the hard carbon negative electrode composite material according to claim 1, wherein the hard carbon precursor, the lithium-containing compound and the binder are mixed mechanically at a temperature of 150 ℃ to 250 ℃ and at a rotation speed of 10rpm to 200 rpm.
3. The preparation method of the hard carbon negative electrode composite material according to claim 1, wherein the sintering treatment temperature is 700 ℃ to 1000 ℃, the heating rate is 2 ℃/min to 10 ℃/min, and the heat preservation time is 1h to 6 h.
4. The method for preparing the hard carbon anode composite material according to claim 1, wherein the carbonaceous raw material is selected from a mixture of one or more of a polymer-based material, a coal-based material and a biomass-based material; and/or
The lithium-containing compound is selected from one or a mixture of more of lithium carbonate, lithium hydroxide, lithium nitrate, lithium oxalate, lithium chloride, lithium sulfide, lithium fluoride, lithium acetate, lithium oxide, lithium hexafluorophosphate and lithium tetrafluoroborate; and/or
The binder is selected from one or a mixture of more of asphalt, heavy oil, coal tar, polytetrafluoroethylene, polyvinylidene fluoride and hydrocarbons with the carbon number of 6-14.
5. The method for preparing the hard carbon negative electrode composite material as claimed in claim 4, wherein the mass ratio of the hard carbon precursor, the lithium-containing compound and the binder is (72-94): (5-23): 1-5).
6. The method for preparing the hard carbon anode composite material according to claim 1, wherein the carbon coating treatment is selected from liquid phase coating or gas phase coating;
when the carbon coating is liquid phase coating, the liquid phase coated carbon source is selected from one or a mixture of more of coal tar, paraffin, liquid hydrocarbons, heavy oil and derivatives thereof, sucrose, glucose and polyvinylidene fluoride; after the step of carbon coating, the obtained product is carbonized at the temperature of 700-1200 ℃ for 1-5 h;
when the carbon coating is gas phase coating, the gas phase coating is chemical gas phase coating or physical gas phase coating; the carbon source coated by the chemical gas phase is one or more of mixed gas of propyne, propylene, methane, ethane, propane, ethylene, acetylene, benzene, toluene, xylene, styrene and ethylbenzene, the temperature of the chemical gas phase coating is 700-1000 ℃, and the time is 0.5-6 h.
7. The method for preparing a hard carbon negative electrode composite material according to any one of claims 1 to 6, wherein the carbon coating layer accounts for 0.1 to 5% by weight of the hard carbon negative electrode composite material, the pre-lithiated hard carbon has a median particle diameter of 5 to 30 μm, and the carbon coating layer has a thickness of 5 to 1000 nm.
8. The method of preparing a hard carbon anode composite according to claim 7, wherein the pre-treatment of the carbonaceous feedstock comprises: carrying out crushing treatment and heat treatment on the carbon-containing raw material;
the heat treatment is carried out in oxygen-containing atmosphere, the temperature of the heat treatment is 150-300 ℃, and the time is 5-24 h.
9. A hard carbon anode composite material prepared by the method for preparing a hard carbon anode composite material according to any one of claims 1 to 8.
10. A lithium secondary battery characterized in that its negative electrode comprises the hard carbon negative electrode composite material according to claim 9.
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