CN115566170B - Preparation method of high-energy-density quick-charging lithium ion battery anode material - Google Patents
Preparation method of high-energy-density quick-charging lithium ion battery anode material Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010405 anode material Substances 0.000 title abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 33
- 239000010439 graphite Substances 0.000 claims abstract description 33
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007770 graphite material Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011366 tin-based material Substances 0.000 claims abstract description 20
- 238000009689 gas atomisation Methods 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000007773 negative electrode material Substances 0.000 claims description 16
- 238000012546 transfer Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical group CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical group [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- HVYYTJFWIYJPFE-UHFFFAOYSA-J 2-hydroxypropane-1-sulfonate tin(4+) Chemical compound [Sn+4].CC(O)CS([O-])(=O)=O.CC(O)CS([O-])(=O)=O.CC(O)CS([O-])(=O)=O.CC(O)CS([O-])(=O)=O HVYYTJFWIYJPFE-UHFFFAOYSA-J 0.000 claims description 2
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 2
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 claims description 2
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 1
- BJDDAXVXMQYXHL-UHFFFAOYSA-J tris(ethylsulfonyloxy)stannyl ethanesulfonate Chemical compound [Sn+4].CCS([O-])(=O)=O.CCS([O-])(=O)=O.CCS([O-])(=O)=O.CCS([O-])(=O)=O BJDDAXVXMQYXHL-UHFFFAOYSA-J 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 26
- 239000002131 composite material Substances 0.000 abstract description 25
- 238000005530 etching Methods 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 238000012360 testing method Methods 0.000 description 23
- 229910003481 amorphous carbon Inorganic materials 0.000 description 18
- 239000007788 liquid Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910021383 artificial graphite Inorganic materials 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000003860 storage Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000005234 chemical deposition Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- -1 2-propanediol Chemical compound 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XDJYNCLHESNUHA-UHFFFAOYSA-J 2-hydroxyethanesulfonate tin(4+) Chemical compound [Sn+4].OCCS([O-])(=O)=O.OCCS([O-])(=O)=O.OCCS([O-])(=O)=O.OCCS([O-])(=O)=O XDJYNCLHESNUHA-UHFFFAOYSA-J 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910004403 Li(Ni0.6Co0.2Mn0.2)O2 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
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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
- C01B32/20—Graphite
- C01B32/21—After-treatment
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
Description
技术领域technical field
本发明属于锂离子电池材料制备领域，具体的说是一种高能量密度快充锂离子电池负极材料的制备方法。The invention belongs to the field of preparation of lithium-ion battery materials, in particular to a preparation method of a high-energy-density fast-charge lithium-ion battery negative electrode material.
背景技术Background technique
随着市场对锂离子电池能量密度要求的提高，要求锂离子电池负极材料具有高的能量密度，目前市场化的负极材料主要以人造石墨为主，制备方法主要采用固相或液相法在石墨表面包覆软碳或硬碳提升材料的首次效率及其低温性能，但是存在包覆后降低了材料的比容量和压实密度。而如果与硅基材料混合则会造成材料膨胀较大，影响其循环及高温存储性能。现有的方法是通过材料表面包覆，在不降低材料能量密度的同时，改善材料的内核与外壳的界面阻抗，提升倍率性能。但目前的固相材料包覆由于内核与外壳掺杂物质是两种不同类型的材料，存在包覆均匀性差，致密化度低等缺陷，为解决此缺陷现采用化学沉积法通过化学反应并在其表面进行化学沉积材料，具有沉积均匀性好、过程可控、掺杂均匀等优点，并根据要求，可以沉积不同厚度、不同种类物质以提升材料的功率、循环、高温及其能量密度，灵活性强，制备过程简单等优点。比如专利申请号201110374264.X公开了一种锂离子电池锡基复合负极材料的制备方法，其步骤为：(1)将金属锡粉、石墨、分散剂与水混合形成浆料；(2)喷雾造粒得颗粒；(3)将导电聚合物溶液与所述的颗粒混合，得到锡掺杂石墨复合材料，其复合材料具有400mAh/g以上的放电比容量，首次库伦效率在85％以上，虽然能量密度得到提升，但是存在首次效率低，动力学性能差及其一致性差等缺陷。As the market's requirements for the energy density of lithium-ion batteries increase, lithium-ion battery anode materials are required to have high energy density. At present, the market-oriented anode materials are mainly artificial graphite, and the preparation method mainly adopts solid-phase or liquid-phase method on graphite. The surface coating of soft carbon or hard carbon improves the initial efficiency and low-temperature performance of the material, but the specific capacity and compaction density of the material are reduced after coating. However, if it is mixed with silicon-based materials, it will cause the material to expand greatly, which will affect its cycle and high-temperature storage performance. The existing method is to improve the interface impedance between the core and the shell of the material without reducing the energy density of the material by coating the surface of the material to improve the rate performance. However, the current solid-phase material coating has defects such as poor coating uniformity and low densification because the core and shell dopant substances are two different types of materials. Chemically deposited materials on its surface have the advantages of good deposition uniformity, controllable process, uniform doping, etc., and according to requirements, different thicknesses and different types of substances can be deposited to improve the power, cycle, high temperature and energy density of the material, flexible Strong, simple preparation process and other advantages. For example, Patent Application No. 201110374264.X discloses a preparation method of tin-based composite negative electrode material for lithium-ion batteries. The steps are: (1) mixing metal tin powder, graphite, dispersant and water to form a slurry; (2) spraying (3) the conductive polymer solution is mixed with the particles to obtain a tin-doped graphite composite material, the composite material has a specific discharge capacity of more than 400mAh/g, and the Coulombic efficiency is more than 85% for the first time, although The energy density has been improved, but there are defects such as low initial efficiency, poor kinetic performance and poor consistency.
发明内容Contents of the invention
本发明的目的在于克服上述缺点而提供的一种能提升石墨材料的能量密度及快充性能，首次效率高，且制备过程简单、过程可控、材料来源广泛，成本低的高能量密度快充锂离子电池负极材料的制备方法。The purpose of the present invention is to overcome the above disadvantages and provide a high energy density fast charge that can improve the energy density and fast charge performance of graphite materials, has high initial efficiency, simple preparation process, process controllable, wide source of materials, and low cost. A method for preparing a negative electrode material for a lithium ion battery.
本发明的一种高能量密度快充锂离子电池负极材料的制备方法，包括如下步骤：The preparation method of a kind of high energy density fast charging lithium ion battery negative electrode material of the present invention comprises the following steps:
(1)将有机锡盐添加到聚合物溶液中配制成1-10wt％的溶液，分散均匀后，添加石墨，超声分散，作为反应液A；将还原剂添加到有机溶剂中配制成1-10wt％的溶液B；其中有机锡盐：还原剂：石墨质量比＝1-10:1-10：100；(1) Add organic tin salt to the polymer solution to prepare a 1-10wt% solution. After uniform dispersion, add graphite and ultrasonically disperse it as reaction solution A; add a reducing agent to an organic solvent to prepare a 1-10wt% solution % solution B; wherein organic tin salt: reducing agent: graphite mass ratio=1-10:1-10:100;
(2)将反应液A转移到不锈钢反应釜中，升温到50-100℃，抽真空到真空度为-0.1Mpa后加入溶液B，在搅拌状态下反应1-6h，过滤，滤渣真空干燥，得到锡基材料掺杂石墨材料；(2) Transfer the reaction solution A to a stainless steel reaction kettle, raise the temperature to 50-100°C, evacuate until the vacuum degree is -0.1Mpa, then add solution B, react for 1-6h under stirring, filter, and vacuum-dry the filter residue, Obtain tin-based material doped graphite material;
(3)将锡基材料掺杂石墨材料转移到反应釜中，并通过气体雾化法，采用浓盐酸、浓硝酸、浓硫酸中的一种，在温度30-100℃，压力为1-10MPa对锡基材料掺杂石墨材料进行刻蚀30-300min，去离子水洗涤到Ph＝7、80℃真空干燥24h，800℃碳化3h，得到多孔锡无定形碳包覆石墨复合材料即得。(3) Transfer the tin-based material doped graphite material into the reaction kettle, and use one of concentrated hydrochloric acid, concentrated nitric acid, and concentrated sulfuric acid through the gas atomization method at a temperature of 30-100°C and a pressure of 1-10MPa Etching the tin-based material doped graphite material for 30-300min, washing with deionized water until Ph=7, vacuum drying at 80°C for 24h, and carbonizing at 800°C for 3h to obtain a porous tin amorphous carbon-coated graphite composite material.
所述步骤(1)中有机锡盐为甲磺酸锡、2-羟基乙磺酸锡、2-羟基丙磺酸锡，二甲基锡、二辛基锡、四苯基锡或草酸亚锡中的一种；聚合物为丁二醇、乙二醇、2-丙二醇、丙三醇或季戊四醇中的一种。In the described step (1), the organotin salt is tin methanesulfonate, tin 2-hydroxyethanesulfonate, tin 2-hydroxypropanesulfonate, dimethyl tin, dioctyl tin, tetraphenyl tin or stannous oxalate One; the polymer is one of butanediol, ethylene glycol, 2-propanediol, glycerol or pentaerythritol.
所述步骤(2)中还原剂为水合肼，溶剂为甲醇、乙醇、丙醇、正丁醇或苯甲醇中的一种。In the step (2), the reducing agent is hydrazine hydrate, and the solvent is one of methanol, ethanol, propanol, n-butanol or benzyl alcohol.
所述步骤(3)中硫酸蒸汽中硫酸浓度为20-80wt％，硝酸蒸汽中硝酸浓度为50-80wt％，盐酸蒸汽中盐酸浓度为20-37wt％。In the step (3), the sulfuric acid concentration in the sulfuric acid vapor is 20-80wt%, the nitric acid concentration in the nitric acid vapor is 50-80wt%, and the hydrochloric acid concentration in the hydrochloric acid vapor is 20-37wt%.
本发明与现有技术相比，具有明显有益效果，从以上技术方案可知：本发明通过氧化还原化学沉积法在石墨表面沉积得到锡基材料掺杂石墨材料，依靠其锡的电子导电率的特性，降低阻抗，由于该氧化还原化学沉积法具有沉积均匀、致密度高、过程可控等优点，且锡基化合物通过聚合物的混合，可以使锡基化合物均匀分散。聚合物碳化后留下的孔洞提升了材料的吸液保液性能，且锡与锂形成的合金比碳与锂形成的LiC6消耗较少的锂离子，使其形成SEI膜消耗较少的锂离子，从而提升了首次效率。本发明通过气体雾化法对石墨表面包覆的锡基化合物进行刻蚀得到多孔锡基化合物包覆石墨材料，可以实现材料表面刻蚀，增加了充放电过程中材料的锂离子嵌脱通道，从而提升材料的动力学性能。同时，多孔锡基化合物含有锡化合物和无定形碳，产生协同作用，利用多孔锡化合物的电子导电性和多孔结构提升保液，并提升材料的离子导电性。无定形碳具有加工性能好，且锡化合物是通过氧化还原反应，使锡化合物掺杂包覆在石墨表面具有结构稳定，掺杂均匀性好等特性。同时，制备过程简单、过程可控、材料来源广泛，成本低，适合产业化生产。Compared with the prior art, the present invention has obvious beneficial effects. From the above technical solutions, it can be known that the present invention deposits tin-based material doped graphite material on the surface of graphite by oxidation-reduction chemical deposition method, relying on the characteristics of the electronic conductivity of tin , to reduce impedance, because the redox chemical deposition method has the advantages of uniform deposition, high density, process control, etc., and the tin-based compound can be uniformly dispersed through the mixing of the polymer. The pores left after the carbonization of the polymer improve the liquid absorption and retention properties of the material, and the alloy formed by tin and lithium consumes less lithium ions than LiC 6 formed by carbon and lithium, so that the formation of SEI film consumes less lithium ions, thereby improving the first-time efficiency. The present invention etches the tin-based compound coated on the graphite surface by a gas atomization method to obtain a porous tin-based compound-coated graphite material, which can realize material surface etching and increase the lithium ion intercalation and extraction channels of the material during charging and discharging. Thereby improving the dynamic performance of the material. At the same time, the porous tin-based compound contains tin compounds and amorphous carbon, which produces a synergistic effect, utilizing the electronic conductivity and porous structure of the porous tin compounds to enhance liquid retention and improve the ionic conductivity of the material. Amorphous carbon has good processing performance, and the tin compound is doped and coated on the graphite surface through oxidation-reduction reaction, which has the characteristics of stable structure and good doping uniformity. At the same time, the preparation process is simple, the process is controllable, the source of materials is wide, the cost is low, and it is suitable for industrial production.
附图说明Description of drawings
图1为实施例1制备出的多孔锡无定形碳包覆石墨复合材料。Fig. 1 is the porous tin amorphous carbon coated graphite composite material prepared in Example 1.
具体实施方式Detailed ways
实施例1Example 1
一种高能量密度快充锂离子电池负极材料的制备方法，包括如下步骤：A method for preparing a negative electrode material for fast-charging lithium-ion batteries with high energy density, comprising the steps of:
(1)将5g甲磺酸锡添加到100g丁二醇溶液中配制成5wt％的浓度，分散均匀后，添加100g人造石墨，超声分散，作为反应液A；将5g水合肼添加到100g乙醇溶剂中配制成质量浓度5wt％的溶液B；(1) 5g tin methanesulfonate is added in 100g butanediol solution and is mixed with the concentration of 5wt%, after dispersing evenly, add 100g artificial graphite, ultrasonic dispersion, as reaction solution A; 5g hydrazine hydrate is added to 100g ethanol solvent be prepared into solution B with a mass concentration of 5wt%;
(2)将反应液A转移到不锈钢反应釜中，升温到80℃，抽真空到真空度为-0.1Mpa后加入溶液B，在搅拌状态下反应3h，过滤，滤渣80℃真空干燥24h，得到锡基材料掺杂石墨材料；(2) Transfer the reaction solution A to a stainless steel reaction kettle, raise the temperature to 80°C, evacuate until the vacuum degree is -0.1Mpa, add solution B, react under stirring for 3h, filter, and vacuum-dry the filter residue at 80°C for 24h to obtain Tin-based materials doped with graphite materials;
(3)将锡基材料掺杂石墨材料转移到反应釜中，并通过气体雾化法，采用浓盐酸(质量浓度30％)，在温度50℃，压力为5MPa对锡基材料掺杂石墨材料进行刻蚀300min，洗涤、80℃真空干燥24h，800℃碳化3h，得到多孔锡无定形碳包覆石墨复合材料即得。(3) transfer the tin-based material doped graphite material to the reaction kettle, and adopt concentrated hydrochloric acid (mass concentration 30%) by gas atomization method, at a temperature of 50 ° C, a pressure of 5 MPa to the tin-based material doped graphite material Etching for 300 minutes, washing, vacuum drying at 80°C for 24 hours, and carbonization at 800°C for 3 hours to obtain a porous tin amorphous carbon-coated graphite composite material.
实施例2Example 2
一种高能量密度快充锂离子电池负极材料的制备方法，包括如下步骤：A method for preparing a negative electrode material for fast-charging lithium-ion batteries with high energy density, comprising the steps of:
(1)将1g 2-羟基乙磺酸锡添加到100g 2-丙二醇溶液中配制成1wt％的溶液，分散均匀后，添加100g人造石墨，超声分散，作为反应液A；将10g水合肼添加到100g甲醇有机溶剂中配制成质量浓度10wt％的溶液B；(1) 1g 2-hydroxyethanesulfonate is added in 100g 2-propanediol solution and is mixed with the solution of 1wt%, after dispersing evenly, add 100g artificial graphite, ultrasonic dispersion, as reaction solution A; 10g hydrazine hydrate is added to 100g methanol organic solvent is prepared into solution B with a mass concentration of 10wt%;
(2)将反应液A转移到不锈钢反应釜中，升温到50℃，抽真空到真空度为-0.1Mpa后加入溶液B，在搅拌状态下反应6h，过滤，滤渣80℃真空干燥24h，得到锡基材料掺杂石墨材料；(2) Transfer the reaction solution A to a stainless steel reaction kettle, heat up to 50°C, evacuate until the vacuum degree is -0.1Mpa, add solution B, react under stirring for 6h, filter, and vacuum-dry the filter residue at 80°C for 24h to obtain Tin-based materials doped with graphite materials;
(3)将锡基材料掺杂石墨材料转移到反应釜中，并通过气体雾化法，采用浓硝酸(质量浓度60％)，在温度30℃，压力为10MPa对锡基材料掺杂石墨材料进行刻蚀300min，洗涤、80℃真空干燥24h，800℃碳化3h，得到多孔锡无定形碳包覆石墨复合材料即得。(3) transfer the tin-based material doped graphite material to the reaction kettle, and adopt concentrated nitric acid (mass concentration 60%) by gas atomization method, at a temperature of 30°C, a pressure of 10MPa to tin-based material doped graphite material Etching for 300 minutes, washing, vacuum drying at 80°C for 24 hours, and carbonization at 800°C for 3 hours to obtain a porous tin amorphous carbon-coated graphite composite material.
实施例3Example 3
一种高能量密度快充锂离子电池负极材料的制备方法，包括如下步骤：A method for preparing a negative electrode material for fast-charging lithium-ion batteries with high energy density, comprising the steps of:
(1)将10g草酸亚锡添加到100g丙三醇溶液中配制成10wt％的浓度的溶液，分散均匀后，添加100g人造石墨，超声分散，作为反应液A；将1g水合肼添加到100g正丁醇有机溶剂中配制成质量浓度1wt％的溶液B；(1) 10g stannous oxalate is added in 100g glycerol solution and is mixed with the solution of the concentration of 10wt%, after dispersing evenly, add 100g artificial graphite, ultrasonic dispersion, as reaction solution A; Add 1g hydrazine hydrate to 100g normal Prepare solution B with a mass concentration of 1wt% in butanol organic solvent;
(2)将反应液A转移到不锈钢反应釜中，升温到100℃，抽真空到真空度为-0.1Mpa后加入溶液B，在搅拌状态下反应1h，过滤，滤渣80℃真空干燥24h，得到锡基材料掺杂石墨材料；(2) Transfer the reaction solution A to a stainless steel reaction kettle, heat up to 100°C, evacuate to -0.1Mpa, then add solution B, react for 1h under stirring, filter, and vacuum-dry the filter residue at 80°C for 24h to obtain Tin-based materials doped with graphite materials;
(3)将锡基材料掺杂石墨材料转移到反应釜中，并通过气体雾化法，采用浓硫酸(质量浓度60％)，在温度100℃，压力为1MPa对锡基材料掺杂石墨材料进行刻蚀30min，洗涤、80℃真空干燥24h，800℃碳化3h，得到多孔锡无定形碳包覆石墨复合材料即得。(3) transfer the tin-based material doped graphite material to the reaction kettle, and adopt the gas atomization method, adopt concentrated sulfuric acid (mass concentration 60%), at temperature 100 ℃, pressure is 1MPa to tin-based material doped graphite material Perform etching for 30 minutes, wash, vacuum dry at 80°C for 24 hours, and carbonize at 800°C for 3 hours to obtain a porous tin amorphous carbon-coated graphite composite material.
对比例1：Comparative example 1:
一种多孔锡无定形碳包覆石墨复合材料的制备方法，包括如下步骤：A preparation method of porous tin amorphous carbon coated graphite composite material, comprising the steps of:
将1g锡粉、5g沥青与100g人造石墨添加到球磨机中分散均匀后，之后在氩气惰性气氛下加热到900℃碳化3h，粉碎得到锡掺杂石墨材料；之后将锡基材料掺杂石墨材料转移到反应釜中，并通过气体雾化法，采用浓盐酸(质量浓度30％)，在温度50℃，压力为5MPa对锡基材料掺杂石墨材料进行刻蚀300min，去离子水洗涤、滤渣80℃真空干燥24h，800℃碳化3h，得到多孔锡无定形碳包覆石墨复合材料。Add 1g of tin powder, 5g of pitch and 100g of artificial graphite to a ball mill and disperse evenly, then heat to 900°C for 3 hours under an inert argon atmosphere, and then pulverize to obtain tin-doped graphite material; then, tin-based material is doped with graphite material Transfer to the reactor, and adopt concentrated hydrochloric acid (mass concentration 30%) by gas atomization method, at temperature 50 ℃, pressure is 5MPa to etch tin-based material doped graphite material for 300min, wash with deionized water, filter residue Vacuum drying at 80°C for 24h and carbonization at 800°C for 3h to obtain a porous tin amorphous carbon-coated graphite composite material.
对比例2：Comparative example 2:
一种多孔锡无定形碳包覆石墨复合材料的制备方法，包括如下步骤：A preparation method of porous tin amorphous carbon coated graphite composite material, comprising the steps of:
采用实施例1步骤(2)中制备出的锡基材料掺杂石墨材料作为负极，不进行表面刻蚀。The tin-based material doped graphite material prepared in step (2) of Example 1 was used as the negative electrode without surface etching.
试验例：Test example:
1.SEM测试1. SEM test
对实施例1得到的多孔锡无定形碳包覆石墨复合材料进行SEM测试，测试结果如图1所示。由图1可知，该材料颗粒大小分布均匀、合理，颗粒粒径介于10-15μm之间,其材料表面有多孔结构。The porous tin amorphous carbon-coated graphite composite material obtained in Example 1 was tested by SEM, and the test results are shown in FIG. 1 . It can be seen from Figure 1 that the particle size distribution of the material is uniform and reasonable, the particle size is between 10-15 μm, and the surface of the material has a porous structure.
2.扣式电池测试2. Button battery test
将实施例1-3及对比例1-2中得到的多孔锡无定形碳包覆石墨复合材料作为锂离子电池负极材料组装成扣式电池。The porous tin amorphous carbon-coated graphite composite materials obtained in Examples 1-3 and Comparative Examples 1-2 were used as negative electrode materials for lithium-ion batteries to assemble button batteries.
具体制备方法为：在锂离子电池负极材料中添加粘结剂、导电剂及溶剂，进行搅拌制浆，涂覆在铜箔上，经过烘干、碾压制得负极片；所用粘结剂为LA132，导电剂为到导电炭黑(SP)，溶剂为N-甲基吡咯烷酮(NMP)，负极材料、SP、LA132、NMP的用量比例为95g：1g：4g：220mL；电解液中LiPF6为电解质，体积比为1:1的EC和DEC的混合物为溶剂；金属锂片为对电极，隔膜采用聚丙烯(PP)膜。扣式电池装配在充氩气的手套箱中进行。电化学性能在武汉蓝电CT2001A型电池测试仪上进行，充放电电压范围为0.005V-2.0V，充放电速率为0.1C。同时测试其倍率(2C/0.1C)和循环性能(0.2C/0.2C，100周)测试结果如表1所示。The specific preparation method is: add binder, conductive agent and solvent to the negative electrode material of lithium ion battery, carry out stirring slurry, coat on the copper foil, dry, roll and press to obtain the negative electrode sheet; the binder used is For LA132, the conductive agent is conductive carbon black (SP), the solvent is N-methylpyrrolidone (NMP), and the dosage ratio of negative electrode material, SP, LA132, and NMP is 95g: 1g: 4g: 220mL; LiPF 6 in the electrolyte is The electrolyte is a mixture of EC and DEC with a volume ratio of 1:1 as the solvent; the metal lithium sheet is used as the counter electrode, and the diaphragm is made of polypropylene (PP) film. Coin cell assembly was performed in an argon-filled glove box. The electrochemical performance was carried out on Wuhan Landian CT2001A battery tester, the charge and discharge voltage range was 0.005V-2.0V, and the charge and discharge rate was 0.1C. At the same time, the rate (2C/0.1C) and cycle performance (0.2C/0.2C, 100 weeks) test results are shown in Table 1.
表1Table 1
由表1中的数据可以看出，本发明实施例1-3制备出多孔锡无定形碳包覆石墨复合材料的首次放电比容量及其首次效率优于对比例。其原因为实施例采用化学沉积法在其石墨表面均匀包覆网状结构锡基化合物，碳化后得到多孔结构的多孔锡，具有均匀性好、致密度高、阻抗低等优点，降低极化，提升材料的放电比容量发挥和首次效率的提高。It can be seen from the data in Table 1 that the first discharge specific capacity and first discharge efficiency of the porous tin amorphous carbon-coated graphite composite material prepared in Examples 1-3 of the present invention are better than those of the comparative examples. The reason is that the embodiment adopts the chemical deposition method to evenly coat the network structure tin-based compound on the graphite surface, and obtain porous tin with porous structure after carbonization, which has the advantages of good uniformity, high density, low impedance, etc., and reduces polarization. Improve the discharge specific capacity of the material and the improvement of the first efficiency.
3.软包电池测试3. Soft pack battery test
将实施例1-3及对比例1-2中的多孔锡无定形碳包覆石墨复合材料作为负极材料制得负极片，以三元材料(Li(Ni0.6Co0.2Mn0.2)O2)为正极材料；电解液中LiPF6为电解质，体积比为1:1的碳酸乙烯酯(EC)和碳酸二乙酯(DEC)的混合物为溶剂；以Celgard 2400膜为隔膜，制备出5Ah软包电池，标记为C1、C2、C3和D1，D2。The porous tin amorphous carbon-coated graphite composite material in Examples 1-3 and Comparative Examples 1-2 was used as the negative electrode material to prepare the negative electrode sheet, and the ternary material (Li(Ni 0.6 Co 0.2 Mn 0.2 )O 2 ) was used as Positive electrode material; LiPF 6 in the electrolyte is used as the electrolyte, and a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) with a volume ratio of 1:1 is used as the solvent; Celgard 2400 film is used as the diaphragm to prepare a 5Ah soft pack battery , labeled C1, C2, C3 and D1, D2.
3.1吸液能力、保液率测试3.1 Test of liquid absorption capacity and liquid retention rate
3.1.1吸液能力3.1.1 Liquid absorption capacity
采用1mL的滴定管，并吸取电解液VmL，在极片表面滴加一滴，并进行计时，直至电解液吸收完毕，记下时间t，计算极片的吸液速度V/t。测试结果如表2所示。Use a 1mL burette to absorb the electrolyte VmL, drop a drop on the surface of the pole piece, and count the time until the electrolyte is absorbed, record the time t, and calculate the liquid absorption speed V/t of the pole piece. The test results are shown in Table 2.
3.1.2保液率测试3.1.2 Liquid retention test
按照极片参数计算出极片的理论吸液量m1，并称取极片的重量m2，之后将极片放置到电解液中浸泡24h，称取极片的重量为m3，计算出极片吸液量m3-m2，并按照下式计算：保液率＝(m3-m2)*100％/m1。测试结果如表2所示。Calculate the theoretical liquid absorption m 1 of the pole piece according to the parameters of the pole piece, and weigh the weight m 2 of the pole piece, then place the pole piece in the electrolyte solution for 24 hours, weigh the weight of the pole piece as m 3 , and calculate The liquid absorption of the pole piece is m 3 -m 2 , and is calculated according to the following formula: liquid retention rate=(m 3 -m 2 )*100%/m 1 . The test results are shown in Table 2.
3.2极片电阻率、反弹率测试3.2 Electrode resistivity and rebound rate test
3.2.1极片电阻率测试3.2.1 Electrode resistivity test
采用电阻率测试仪测试极片的电阻率，测试结果如表3所示。A resistivity tester was used to test the resistivity of the pole pieces, and the test results are shown in Table 3.
3.2.2极片反弹率测试3.2.2 Electrode rebound rate test
首先采用测厚仪测试其极片的平均厚度为D1，之后将极片放置在80℃的真空干燥箱中干燥48h，测试极片的厚度为D2，并按下式计算：反弹率＝(D2-D1)*100％/D1。测试结果如表3所示。First use a thickness gauge to test the average thickness of the pole piece as D1, then place the pole piece in a vacuum oven at 80°C to dry for 48 hours, test the thickness of the pole piece as D2, and calculate according to the following formula: rebound rate = (D2 -D1)*100%/D1. The test results are shown in Table 3.
3.3循环性能测试3.3 Cycle performance test
以充放电倍率为1C/1C、电压范围为2.8V-4.2V，在温度25±3℃下测试电池的循环性能。测试结果如表4所示。The cycle performance of the battery was tested at a temperature of 25±3°C with a charge-discharge rate of 1C/1C and a voltage range of 2.8V-4.2V. The test results are shown in Table 4.
3.5高温存储3.5 High temperature storage
将电池充电到100％SOC，并测试其电池的容量为M1；之后放置到温度为55℃的烘箱中7天，之后测试其电池的容量为M2；之后对其电池充电到100％SOC，测试其电池的容量为M3；最后计算出电池的荷电保持＝M2/M1*100％，容量恢复＝M3/M1*100％。测试结果详见表4。Charge the battery to 100% SOC, and test the capacity of the battery as M1; then place it in an oven at a temperature of 55°C for 7 days, and then test the capacity of the battery as M2; then charge the battery to 100% SOC, test The capacity of the battery is M3; finally, it is calculated that the charge retention of the battery=M2/M1*100%, and the capacity recovery=M3/M1*100%. The test results are detailed in Table 4.
表2Table 2
从表2可以看出，实施例1-3所得多孔锡无定形碳包覆石墨复合材料的吸液保液能力明显高于对比例。实验结果表明，本发明提供的石墨复合负极材料具有较高的吸液保液能力。这主要是因为本发明提供的石墨复合负极材料的具有高的比表面积，提升材料的吸液保液能力。It can be seen from Table 2 that the liquid absorption and retention capacity of the porous tin amorphous carbon-coated graphite composite material obtained in Examples 1-3 is significantly higher than that of the comparative examples. Experimental results show that the graphite composite negative electrode material provided by the invention has a relatively high ability to absorb and retain liquid. This is mainly because the graphite composite negative electrode material provided by the present invention has a high specific surface area, which improves the liquid absorption and retention capacity of the material.
表3table 3
从表3中数据可以看出，采用实施例1-3所得多孔锡无定形碳包覆石墨复合材料制备的负极片反弹率明显低于对比例，即采用本发明的多孔锡无定形碳包覆石墨复合材料制得的负极片具有较低的反弹率。这是因为本发明化学沉淀法和气体雾化法具有致密度高，多孔结构的包覆层束缚材料的膨胀；同时依靠包覆电子导电率高的锡降低阻抗，并降低极片电阻率。As can be seen from the data in Table 3, the rebound rate of the negative electrode sheet prepared by using the porous tin amorphous carbon coated graphite composite material obtained in Examples 1-3 is significantly lower than that of the comparative example, that is, the porous tin amorphous carbon coated graphite composite material of the present invention is adopted. The negative electrode sheet made of graphite composite material has a lower rebound rate. This is because the chemical precipitation method and the gas atomization method of the present invention have a high density, and the coating layer of the porous structure restrains the expansion of the material; at the same time, relying on the tin with high electronic conductivity to reduce the impedance and reduce the resistivity of the pole piece.
表4Table 4
由表4可以看出，本发明提供的多孔锡无定形碳包覆石墨复合材料制得的电池的循环性能明显优于对比例。这是因为本发明提供的石墨复合负极材料制得的极片具有较低的膨胀率，在充放电过程中极片的结构更加稳定，提高了其循环性能。同时多孔结构虽然降低高温存储性能，但是由于实施例材料内核与外壳之间的界面阻抗低及其膨胀低，提升其高温存储性能。It can be seen from Table 4 that the cycle performance of the battery made of the porous tin amorphous carbon-coated graphite composite material provided by the present invention is obviously better than that of the comparative example. This is because the electrode sheet made of the graphite composite negative electrode material provided by the present invention has a lower expansion rate, and the structure of the electrode sheet is more stable during the charging and discharging process, which improves its cycle performance. At the same time, although the porous structure reduces the high-temperature storage performance, the high-temperature storage performance is improved due to the low interface resistance and low expansion between the core and the shell of the material of the embodiment.
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。The above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Anyone skilled in the art can easily think of changes or substitutions within the technical scope disclosed in the present invention. Should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.
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Application publication date: 20230103 Assignee: Guizhou Huiyang Technology Innovation Research Co.,Ltd. Assignor: Huiyang (Guizhou) new energy materials Co.,Ltd. Contract record no.: X2024980031240 Denomination of invention: Preparation method of negative electrode material for high-energy density fast charging lithium-ion batteries Granted publication date: 20230718 License type: Common License Record date: 20241202 |