CN113651307B - Sodium-ion battery carbon negative electrode material prepared based on waste sawdust and its preparation method - Google Patents
Sodium-ion battery carbon negative electrode material prepared based on waste sawdust and its preparation method Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 14
- 239000002699 waste material Substances 0.000 title claims abstract description 13
- 239000007773 negative electrode material Substances 0.000 title abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 52
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- 239000002023 wood Substances 0.000 claims abstract description 30
- 239000002028 Biomass Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000428 dust Substances 0.000 claims abstract description 14
- 238000000197 pyrolysis Methods 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000010406 cathode material Substances 0.000 claims abstract 5
- 239000003575 carbonaceous material Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 18
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 17
- 244000082946 Tarchonanthus camphoratus Species 0.000 claims description 17
- 235000005701 Tarchonanthus camphoratus Nutrition 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 235000009496 Juglans regia Nutrition 0.000 claims description 8
- 238000009656 pre-carbonization Methods 0.000 claims description 7
- 235000020234 walnut Nutrition 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011267 electrode slurry Substances 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 240000007049 Juglans regia Species 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 2
- 238000000227 grinding Methods 0.000 claims 2
- 238000004321 preservation Methods 0.000 claims 2
- 235000006667 Aleurites moluccana Nutrition 0.000 claims 1
- 240000000233 Melia azedarach Species 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 238000011534 incubation Methods 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 230000007547 defect Effects 0.000 abstract description 7
- 238000005087 graphitization Methods 0.000 abstract description 6
- 239000011229 interlayer Substances 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 4
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- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
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- 230000007935 neutral effect Effects 0.000 description 12
- 238000005554 pickling Methods 0.000 description 11
- 235000021110 pickles Nutrition 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 241000758789 Juglans Species 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000003780 insertion Methods 0.000 description 5
- 230000037431 insertion Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 244000237986 Melia azadirachta Species 0.000 description 3
- 235000013500 Melia azadirachta Nutrition 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 241000723422 Catalpa Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 240000000560 Citrus x paradisi Species 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/58—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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Description
技术领域Technical field
本发明属于钠离子电池电极材料制备领域，特别涉及一种基于废弃木屑制备高首效钠离子电池碳负极材料的方法，以及由该制备方法获得的钠离子电池碳负极材料。The invention belongs to the field of sodium-ion battery electrode material preparation, and particularly relates to a method for preparing high-efficiency sodium-ion battery carbon negative electrode materials based on waste wood chips, and a sodium-ion battery carbon negative electrode material obtained by the preparation method.
背景技术Background technique
随着人类社会的快速发展和传统化石能源的消耗，能源危机和环境污染问题持续加剧，因此，开发高效的能源转换方法和清洁能源***尤为重要。目前，锂离子电池因其功率和能量密度高、循环寿命长、安全性好等优点，已成为具有竞争力的新型能源***，广泛应用于智能手机、笔记本电脑、电动汽车等日常生活中。然而，由于迫切需要开发大规模储能设备，而锂资源储量有限，需要开发锂离子电池的替代品来满足未来发展的需要。钠是自然界中广泛分布的一种元素，它比地壳中的锂更丰富、更容易获得，在物理和化学性质上与锂元素相似。钠离子电池(SIBs)引起了研究人员的广泛关注，被认为是一种很有前途的LIBs替代品。With the rapid development of human society and the consumption of traditional fossil energy, the energy crisis and environmental pollution problems continue to intensify. Therefore, it is particularly important to develop efficient energy conversion methods and clean energy systems. At present, lithium-ion batteries have become a competitive new energy system due to their high power and energy density, long cycle life, and good safety. They are widely used in daily life such as smartphones, laptops, and electric vehicles. However, due to the urgent need to develop large-scale energy storage equipment and limited lithium resource reserves, alternatives to lithium-ion batteries need to be developed to meet the needs of future development. Sodium is an element widely distributed in nature. It is more abundant and easier to obtain than lithium in the earth's crust, and has similar physical and chemical properties to lithium. Sodium-ion batteries (SIBs) have attracted widespread attention from researchers and are considered to be a promising alternative to LIBs.
在钠离子电池(SIBs)的研究中，寻找高性能的电极材料具有重要的意义。目前还缺乏适合SIBs的负极材料，这是制约其发展的一个因素。在以往的研究中，碳材料因其优良的导电性、丰富的储量和低廉的成本在电化学能源***中得到了广泛的应用，被认为是最有前途的电极材料。石墨作为一种传统的碳材料，由于其优良的电化学性能，在锂离子电池中得到了广泛的应用。但是，由于钠离子半径大，电离势高，石墨负极材料储钠性能较差。硬碳是指在2500℃以上的温度下难以石墨化的碳，是由随机取向、有缺陷的石墨离散碎片组成，其结构称为“纸牌屋”模型。与石墨相比，硬碳具有更大的层间距和更多的缺陷，显示了低电位(~0.1)和高容量的优点。In the research of sodium-ion batteries (SIBs), it is of great significance to find high-performance electrode materials. There is currently a lack of anode materials suitable for SIBs, which is a factor restricting their development. In previous research, carbon materials have been widely used in electrochemical energy systems due to their excellent conductivity, abundant reserves, and low cost, and are considered to be the most promising electrode materials. Graphite, as a traditional carbon material, has been widely used in lithium-ion batteries due to its excellent electrochemical properties. However, due to the large radius of sodium ions and high ionization potential, graphite anode materials have poor sodium storage performance. Hard carbon refers to carbon that is difficult to graphitize at temperatures above 2500°C. It is composed of randomly oriented, defective discrete fragments of graphite, and its structure is called a "house of cards" model. Compared with graphite, hard carbon has larger interlayer spacing and more defects, showing the advantages of low potential (~0.1) and high capacity.
生物质材料作为制备硬碳的前体之一，由于其成本低、可再生和环境友好的优点，被认为是可靠的大规模碳源。稻壳、柚皮、甘蔗渣、香蕉皮、玉米芯等生物质碳材料已被证明具有良好的储钠性能。首次库仑效率(ICE)决定了实际应用中阳极材料的可用能量密度，是硬碳在SIBs中实现产业化应用的重要因素之一。由于不可逆的钠储存位点、副反应和固体电解质界面相(SEI)的形成，大多数硬碳表现出较低的ICE。为了提高硬碳负极材料的ICE,天津大学的朱等采用热解与H2还原相结合的方法制备硬碳材料。在研究中，H2还原处理显著降低了硬碳中的氧含量，减少了材料的缺陷和不必要的副反应的发生，进一步提高了材料的储钠性能，有效提高了硬碳的ICE。研究人员发现造成硬碳材料首次库伦效率低的是由于在首次放电过程中钠离子的不可逆嵌入，比表面积、缺陷浓度、杂原子含量等是影响其主要因素，高首效生物质硬碳材料的研究开发具有重要的意义。Biomass materials, as one of the precursors for the preparation of hard carbon, are considered to be reliable large-scale carbon sources due to their low cost, renewable and environmentally friendly advantages. Biomass carbon materials such as rice husks, grapefruit peels, sugarcane bagasse, banana peels, and corn cobs have been proven to have good sodium storage properties. The first coulombic efficiency (ICE) determines the available energy density of anode materials in practical applications and is one of the important factors for the industrial application of hard carbon in SIBs. Most hard carbons exhibit lower ICE due to irreversible sodium storage sites, side reactions, and the formation of solid electrolyte interfacial phase (SEI). In order to improve the ICE of hard carbon anode materials, Zhu et al. from Tianjin University used a method combining pyrolysis and H reduction to prepare hard carbon materials. In the study, H2 reduction treatment significantly reduced the oxygen content in hard carbon, reduced material defects and the occurrence of unnecessary side reactions, further improved the material's sodium storage performance, and effectively improved the ICE of hard carbon. Researchers found that the low first Coulombic efficiency of hard carbon materials is due to the irreversible insertion of sodium ions during the first discharge process. Specific surface area, defect concentration, heteroatom content, etc. are the main factors affecting it. High first efficiency biomass hard carbon materials Research and development are of great significance.
发明内容Contents of the invention
本发明所要解决的技术问题是提供一种基于废弃木屑制备的高首效钠离子电池碳负极材料及其制备方法。所制备的硬碳材料具有较低的缺陷浓度、合适的层间距以及较高的石墨化程度，这种特殊的结构有利于钠离子的嵌入和脱出，有效提高材料的首次库伦效率。The technical problem to be solved by the present invention is to provide a high-efficiency sodium-ion battery carbon negative electrode material prepared based on waste wood chips and a preparation method thereof. The prepared hard carbon material has a low defect concentration, suitable interlayer spacing, and a high degree of graphitization. This special structure is conducive to the insertion and extraction of sodium ions, effectively improving the first Coulombic efficiency of the material.
为解决以上技术问题，根据本发明的一个方面，提供一种基于废弃木屑制备钠离子电池碳负极材料的方法，包括：In order to solve the above technical problems, according to one aspect of the present invention, a method for preparing carbon negative electrode materials for sodium ion batteries based on waste wood chips is provided, including:
步骤一：将废弃木屑生物质原料进行超声洗涤预处理去除表面灰尘杂质，干燥后获得生物质前驱体；Step 1: Perform ultrasonic washing pretreatment on waste sawdust biomass raw materials to remove surface dust and impurities, and obtain a biomass precursor after drying;
步骤二：将处理后的生物质前驱体转移至马弗炉中在空气的气氛下进行预碳化，预碳化的升温速率为1-20℃/min，热解温度为200-400℃，保温时间为1-5小时；自然降温冷却后放置于粉碎机中，粉碎至粉末状，得到预碳化产物；Step 2: Transfer the treated biomass precursor to a muffle furnace for pre-carbonization in an air atmosphere. The heating rate of pre-carbonization is 1-20°C/min, the pyrolysis temperature is 200-400°C, and the holding time is It takes 1-5 hours; after natural cooling, it is placed in a pulverizer and pulverized into powder to obtain a pre-carbonized product;
步骤三：将预碳化产物转移到高温管式炉中在惰性气体的保护下高温碳化，高温碳化的升温速率为0.25-1℃/min，热解温度为1200-1400℃，惰性气体选自氮气、氩气、氦气、氢氩混合气（5% H2+95% Ar）中的一种，保温时间为1-10小时；自然降温后研磨、过筛处理；Step 3: Transfer the pre-carbonized product to a high-temperature tube furnace for high-temperature carbonization under the protection of inert gas. The heating rate of high-temperature carbonization is 0.25-1℃/min, and the pyrolysis temperature is 1200-1400℃. The inert gas is selected from nitrogen. , one of argon, helium, hydrogen and argon mixture (5% H 2 +95% Ar), the holding time is 1-10 hours; grind and sieve after natural cooling;
步骤四：将处理后的硬碳材料用酸性溶液洗涤去除金属杂原子，用去离子水和乙醇离心洗涤至中性，烘干后得到硬碳材料。Step 4: Wash the treated hard carbon material with an acidic solution to remove metal heteroatoms, centrifuge and wash with deionized water and ethanol until neutral, and dry to obtain the hard carbon material.
进一步地，步骤一中，所述的废弃木屑为以下乔木类树木木屑中的一种：樟木碎屑、胡桃楸木屑、核桃木屑、榆木屑、苦楝木屑。Further, in step one, the waste wood chips are one of the following arbor tree wood chips: camphor wood chips, walnut wood chips, walnut wood chips, elm wood chips, and neem wood chips.
进一步地，步骤一中，洗涤生物质原料所选用的液体为去离子水、无水乙醇、丙酮中的一种或几种，超声洗涤时间为6-12小时，清洗用液体温度为30-80℃。Further, in step one, the liquid selected for washing the biomass raw materials is one or more of deionized water, absolute ethanol, and acetone. The ultrasonic washing time is 6-12 hours, and the cleaning liquid temperature is 30-80 ℃.
进一步地，步骤二中，预碳化的升温速率为3℃/min，热解温度为300℃，保温时间为2小时。Further, in step two, the pre-carbonization heating rate is 3°C/min, the pyrolysis temperature is 300°C, and the holding time is 2 hours.
进一步地，步骤三中，高温碳化的升温速率为0.25℃/min，热解温度为1300℃，保温时间为2小时。该步骤三中，惰性气体气体流速为10-100 CC/min。降温速率保持在5℃/min。Further, in step three, the heating rate of high-temperature carbonization is 0.25°C/min, the pyrolysis temperature is 1300°C, and the holding time is 2 hours. In step three, the inert gas flow rate is 10-100 CC/min. The cooling rate was maintained at 5°C/min.
进一步地，步骤四中，酸性溶液选自盐酸、硝酸、乙酸、氢氟酸、硫酸中的一种，酸性溶液的浓度为1-5 M，浸泡洗涤时间为1-24小时。Further, in step four, the acidic solution is selected from one of hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid, and sulfuric acid, the concentration of the acidic solution is 1-5 M, and the soaking and washing time is 1-24 hours.
根据本发明的另一方面，提供一种钠离子电池碳负极材料，其特征在于：由以上所述的方法制备获得。According to another aspect of the present invention, a carbon negative electrode material for a sodium ion battery is provided, which is characterized in that it is prepared by the method described above.
根据本发明的另一方面，提供一种硬碳材料电极片，是将以上所述的钠离子电池碳负极材料与乙炔黑、羧甲基纤维素钠和聚丙烯酸按比例研磨均匀，加入去离子水磁力搅拌得到混合均匀的电极浆料，用涂布机将电池浆料均匀涂在铜箔上，放置真空干燥箱中真空干燥小时，然后用冲片机将其制备成圆片电极，得到所属的硬碳材料电极片。According to another aspect of the present invention, a hard carbon material electrode sheet is provided. The above-mentioned sodium ion battery carbon negative electrode material is ground uniformly with acetylene black, sodium carboxymethyl cellulose and polyacrylic acid in proportion, and then deionized is added. Stir with water and magnetic force to obtain a uniformly mixed electrode slurry. Use a coating machine to evenly coat the battery slurry on the copper foil, place it in a vacuum drying box for vacuum drying for an hour, and then use a punching machine to prepare it into a disc electrode to obtain the desired Hard carbon material electrode sheet.
进一步地，乙炔黑、羧甲基纤维素钠和聚丙烯酸的质量比8:1:0.5:0.5。Further, the mass ratio of acetylene black, sodium carboxymethyl cellulose and polyacrylic acid is 8:1:0.5:0.5.
根据本发明的另一方面，提供一种钠离子电池，其包括以上所述的硬碳材料电极片。According to another aspect of the present invention, a sodium ion battery is provided, which includes the above-mentioned hard carbon material electrode sheet.
乔木类树木是指树身高大的树木，主要分布在肥沃土地和温暖区域，分布十分广泛，通常用于园林绿化、建筑和家具制造等。然而，在实际生产中通常会产生大量的废弃木屑，呈现出较低的可利用价值。本发明以废弃木屑为原料，制备工艺流程简单，具有绿色环保、成本低廉等优点，便于进行批量大规模生产。Arbor trees refer to tall trees, mainly distributed in fertile land and warm areas. They are widely distributed and are usually used in landscaping, construction and furniture manufacturing. However, in actual production, a large amount of waste wood chips is usually produced, which presents a low usable value. The invention uses waste wood chips as raw materials, has a simple preparation process, has the advantages of green environmental protection, low cost and other advantages, and is convenient for batch and large-scale production.
本发明通过预碳化和低升温速率热解相结合的方法，其中预碳化的方法使得生物质有机碳链初步形成环结构，同时引入氧基官能团；其中低升温速率热解的方法，可以有效减少硬碳材料的缺陷浓度，硬碳材料表面的部分微孔闭合和比表面积减小，可有效减少硬碳材料不可逆容量的损失，所制备的硬碳材料具有合适的层间距以及较高的石墨化程度，有利于钠离子的嵌入和脱出，具有高首次库伦效率和可逆比容量，其充电曲线为平台型并具有较高的平台容量占比，同时具有优异的循环稳定性和倍率性能，是一种理想的钠离子电池负极材料。The present invention combines pre-carbonization and low heating rate pyrolysis. The pre-carbonization method allows the biomass organic carbon chain to initially form a ring structure and introduces oxygen functional groups at the same time. The low heating rate pyrolysis method can effectively reduce The defect concentration of hard carbon materials, the closure of some micropores on the surface of hard carbon materials and the reduction of specific surface area can effectively reduce the loss of irreversible capacity of hard carbon materials. The prepared hard carbon materials have appropriate layer spacing and high graphitization. degree, which is conducive to the insertion and extraction of sodium ions, has high first Coulombic efficiency and reversible specific capacity, its charging curve is a platform type and has a high platform capacity ratio, and it also has excellent cycle stability and rate performance. It is a An ideal anode material for sodium-ion batteries.
附图说明Description of the drawings
图1是本发明实施例1,2,4和对比例1,2制备的负极材料的XRD图；Figure 1 is the XRD pattern of the negative electrode materials prepared in Examples 1, 2, 4 and Comparative Examples 1, 2 of the present invention;
图2是本发明实施例1,2,4和对比例1,2,制备负极材料的Raman图；Figure 2 is a Raman diagram of the preparation of negative electrode materials in Examples 1, 2, 4 and Comparative Examples 1, 2 of the present invention;
图3是本发明对比例1制备的负极材料的充放电曲线图；Figure 3 is a charge-discharge curve diagram of the negative electrode material prepared in Comparative Example 1 of the present invention;
图4是本发明实施例4制备的负极材料的充放电曲线图；Figure 4 is a charge-discharge curve diagram of the negative electrode material prepared in Example 4 of the present invention;
图5是本发明实施例1,2,4和对比例1,2制备的负极材料的循环性能图；Figure 5 is a cycle performance diagram of the negative electrode materials prepared in Examples 1, 2, 4 and Comparative Examples 1, 2 of the present invention;
图6是本发明实施例4和对比例1制备的负极材料的倍率性能图；Figure 6 is a rate performance diagram of the negative electrode materials prepared in Example 4 and Comparative Example 1 of the present invention;
图7是本发明实施例4制备的负极材料的SEM图；Figure 7 is an SEM image of the negative electrode material prepared in Example 4 of the present invention;
图8是本发明实施例4制备的负极材料的HRTEM图。Figure 8 is an HRTEM image of the negative electrode material prepared in Example 4 of the present invention.
具体实施方式Detailed ways
下面通过一些实施例对本发明要求保护的技术方案作进一步说明。但是，实施例和对比例是用于解释本发明实施方案，并不超出本发明主题的范围，本发明保护范围不受所述实施例的限定。除非另作特殊说明，本发明中所用材料、试剂均可从本领域商业化产品中获得。The technical solution claimed by the present invention will be further described below through some examples. However, the examples and comparative examples are used to explain the embodiments of the present invention and do not exceed the scope of the subject matter of the present invention. The protection scope of the present invention is not limited by the examples. Unless otherwise specified, the materials and reagents used in the present invention can be obtained from commercial products in the field.
实施例1Example 1
步骤一：将生物质樟木木屑用去离子水超声洗涤6小时，去除灰尘杂质，得到的产物在鼓风干燥箱中60℃干燥24小时，去除水分；Step 1: Ultrasonically wash the biomass camphor wood chips with deionized water for 6 hours to remove dust and impurities. The obtained product is dried in a blast drying oven at 60°C for 24 hours to remove moisture;
步骤二：将干燥后的樟木木屑转移至马弗炉中，在空气的气氛下以3℃/min的升温速率升温至300℃保温2小时，随炉自然冷却后取出，用粉碎机将预碳化产物粉碎至粉末状，备用；Step 2: Transfer the dried camphor wood chips to the muffle furnace, heat it to 300℃ at a heating rate of 3℃/min in an air atmosphere and keep it for 2 hours. After natural cooling in the furnace, take it out and crush it with a pulverizer. The carbonized product is crushed to powder and set aside;
步骤三：将预碳化产物放入管式炉中，在惰性气体氩气的保护下，以1℃/min的升温速率由室温25℃升温至1300℃，保温2小时，随炉以5℃/min的降温速率冷却至室温，取出后研磨，并用325目的筛子进行过筛处理；Step 3: Put the pre-carbonized product into a tube furnace, and under the protection of inert gas argon, heat it from room temperature 25°C to 1300°C at a heating rate of 1°C/min, keep it warm for 2 hours, and then heat the furnace at 5°C/min. Cool to room temperature at a cooling rate of min, take it out, grind it, and sieve it with a 325-mesh sieve;
步骤四：将得到的粉末进行酸洗处理，所选的酸洗溶液为2M的稀盐酸溶液，浸泡12小时后用去离子水和乙醇反复离心洗涤至中性，将得到的产物在鼓风干燥箱中80℃干燥12小时，烘干后得到硬碳负极材料。Step 4: Pickle the obtained powder. The selected pickling solution is 2M dilute hydrochloric acid solution. After soaking for 12 hours, use deionized water and ethanol to repeatedly centrifuge and wash until neutral. Dry the obtained product in air. Dry in the box at 80°C for 12 hours, and obtain the hard carbon negative electrode material after drying.
实施例2Example 2
步骤一：将生物质樟木木屑用去离子水超声洗涤6小时，去除灰尘杂质，得到的产物在鼓风干燥箱中60℃干燥24小时，去除水分；Step 1: Ultrasonically wash the biomass camphor wood chips with deionized water for 6 hours to remove dust and impurities. The obtained product is dried in a blast drying oven at 60°C for 24 hours to remove moisture;
步骤二：将干燥后的樟木木屑转移至马弗炉中，在空气的气氛下以3℃/min的升温速率升温至300℃保温2小时，随炉自然冷却后取出，用粉碎机将预碳化产物粉碎至粉末状，备用；Step 2: Transfer the dried camphor wood chips to the muffle furnace, heat it to 300℃ at a heating rate of 3℃/min in an air atmosphere and keep it for 2 hours. After natural cooling in the furnace, take it out and crush it with a pulverizer. The carbonized product is crushed to powder and set aside;
步骤三：将预碳化产物放入管式炉中，在惰性气体氩气的保护下，以0.5℃/min的升温速率由室温25℃升温至1300℃，保温2小时，随炉以5℃/min的降温速率冷却至室温，取出后研磨，并用325目的筛子进行过筛处理；Step 3: Put the pre-carbonized product into a tube furnace, and under the protection of inert gas argon, heat it up from room temperature 25°C to 1300°C at a heating rate of 0.5°C/min, keep it warm for 2 hours, and then heat it up with the furnace at 5°C/min. Cool to room temperature at a cooling rate of min, take it out, grind it, and sieve it with a 325-mesh sieve;
步骤四：将得到的粉末进行酸洗处理，所选的酸洗溶液为2M的稀盐酸溶液，浸泡12小时后用去离子水和乙醇反复离心洗涤至中性，将得到的产物在鼓风干燥箱中80℃干燥12小时，烘干后得到硬碳负极材料。Step 4: Pickle the obtained powder. The selected pickling solution is 2M dilute hydrochloric acid solution. After soaking for 12 hours, use deionized water and ethanol to repeatedly centrifuge and wash until neutral. Dry the obtained product in air. Dry in the box at 80°C for 12 hours, and obtain the hard carbon negative electrode material after drying.
实施例3Example 3
步骤一：将生物质樟木木屑用去离子水超声洗涤6小时，去除灰尘杂质，得到的产物在鼓风干燥箱中60℃干燥24小时，去除水分；Step 1: Ultrasonically wash the biomass camphor wood chips with deionized water for 6 hours to remove dust and impurities. The obtained product is dried in a blast drying oven at 60°C for 24 hours to remove moisture;
步骤二：将干燥后的樟木木屑转移至马弗炉中，在空气的气氛下以3℃/min的升温速率升温至300℃保温2小时，随炉自然冷却后取出，用粉碎机将预碳化产物粉碎至粉末状，备用；Step 2: Transfer the dried camphor wood chips to the muffle furnace, heat it to 300℃ at a heating rate of 3℃/min in an air atmosphere and keep it for 2 hours. After natural cooling in the furnace, take it out and crush it with a pulverizer. The carbonized product is crushed to powder and set aside;
步骤三：将预碳化产物放入管式炉中，在惰性气体氩气的保护下，以0.25℃/min的升温速率由室温25℃升温至1200℃，保温2小时，随炉以5℃/min的降温速率冷却至室温，取出后研磨，并用325目的筛子进行过筛处理；Step 3: Put the pre-carbonized product into a tube furnace, and under the protection of inert gas argon, heat it from room temperature 25°C to 1200°C at a heating rate of 0.25°C/min, keep it warm for 2 hours, and then heat it up with the furnace at 5°C/min. Cool to room temperature at a cooling rate of min, take it out, grind it, and sieve it with a 325-mesh sieve;
步骤四：将得到的粉末进行酸洗处理，所选的酸洗溶液为2M的稀盐酸溶液，浸泡12小时后用去离子水和乙醇反复离心洗涤至中性，将得到的产物在鼓风干燥箱中80℃干燥12小时，烘干后得到硬碳负极材料。Step 4: Pickle the obtained powder. The selected pickling solution is 2M dilute hydrochloric acid solution. After soaking for 12 hours, use deionized water and ethanol to repeatedly centrifuge and wash until neutral. Dry the obtained product in air. Dry in the box at 80°C for 12 hours, and obtain the hard carbon negative electrode material after drying.
实施例4Example 4
步骤一：将生物质樟木木屑用去离子水超声洗涤6小时，去除灰尘杂质，得到的产物在鼓风干燥箱中60℃干燥24小时，去除水分；Step 1: Ultrasonically wash the biomass camphor wood chips with deionized water for 6 hours to remove dust and impurities. The obtained product is dried in a blast drying oven at 60°C for 24 hours to remove moisture;
步骤二：将干燥后的樟木木屑转移至马弗炉中，在空气的气氛下以3℃/min的升温速率升温至300℃保温2小时，随炉自然冷却后取出，用粉碎机将预碳化产物粉碎至粉末状，备用；Step 2: Transfer the dried camphor wood chips to the muffle furnace, heat it to 300℃ at a heating rate of 3℃/min in an air atmosphere and keep it for 2 hours. After natural cooling in the furnace, take it out and crush it with a pulverizer. The carbonized product is crushed to powder and set aside;
步骤三：将预碳化产物放入管式炉中，在惰性气体氩气的保护下，以0.25℃/min的升温速率由室温25℃升温至1300℃，保温2小时，随炉以5℃/min的降温速率冷却至室温，取出后研磨，并用325目的筛子进行过筛处理；Step 3: Put the pre-carbonized product into a tube furnace, and under the protection of inert gas argon, heat it from room temperature 25°C to 1300°C at a heating rate of 0.25°C/min, keep it warm for 2 hours, and then heat it up with the furnace at 5°C/min. Cool to room temperature at a cooling rate of min, take it out, grind it, and sieve it with a 325-mesh sieve;
步骤四：将得到的粉末进行酸洗处理，所选的酸洗溶液为2M的稀盐酸溶液，浸泡12小时后用去离子水和乙醇反复离心洗涤至中性，将得到的产物在鼓风干燥箱中80℃干燥12小时，烘干后得到硬碳负极材料。Step 4: Pickle the obtained powder. The selected pickling solution is 2M dilute hydrochloric acid solution. After soaking for 12 hours, use deionized water and ethanol to repeatedly centrifuge and wash until neutral. Dry the obtained product in air. Dry in the box at 80°C for 12 hours, and obtain the hard carbon negative electrode material after drying.
实施例5Example 5
步骤一：将生物质樟木木屑用去离子水超声洗涤6小时，去除灰尘杂质，得到的产物在鼓风干燥箱中60℃干燥24小时，去除水分；Step 1: Ultrasonically wash the biomass camphor wood chips with deionized water for 6 hours to remove dust and impurities. The obtained product is dried in a blast drying oven at 60°C for 24 hours to remove moisture;
步骤二：将干燥后的樟木木屑转移至马弗炉中，在空气的气氛下以3℃/min的升温速率升温至300℃保温2小时，随炉自然冷却后取出，用粉碎机将预碳化产物粉碎至粉末状，备用；Step 2: Transfer the dried camphor wood chips to the muffle furnace, heat it to 300℃ at a heating rate of 3℃/min in an air atmosphere and keep it for 2 hours. After natural cooling in the furnace, take it out and crush it with a pulverizer. The carbonized product is crushed to powder and set aside;
步骤三：将预碳化产物放入管式炉中，在惰性气体氩气的保护下，以0.25℃/min的升温速率由室温25℃升温至1400℃，保温2小时，随炉以5℃/min的降温速率冷却至室温，取出后研磨，并用325目的筛子进行过筛处理；Step 3: Put the pre-carbonized product into a tube furnace, and under the protection of inert gas argon, heat it from room temperature 25°C to 1400°C at a heating rate of 0.25°C/min, keep it warm for 2 hours, and then heat the furnace at 5°C/min. Cool to room temperature at a cooling rate of min, take it out, grind it, and sieve it with a 325-mesh sieve;
步骤四：将得到的粉末进行酸洗处理，所选的酸洗溶液为2M的稀盐酸溶液，浸泡12小时后用去离子水和乙醇反复离心洗涤至中性，将得到的产物在鼓风干燥箱中80℃干燥12小时，烘干后得到硬碳负极材料。Step 4: Pickle the obtained powder. The selected pickling solution is 2M dilute hydrochloric acid solution. After soaking for 12 hours, use deionized water and ethanol to repeatedly centrifuge and wash until neutral. Dry the obtained product in air. Dry in the box at 80°C for 12 hours, and obtain the hard carbon negative electrode material after drying.
实施例6Example 6
步骤一：将生物质胡桃楸木木屑用无水乙醇超声洗涤12小时，去除灰尘杂质，得到的产物在鼓风干燥箱中30℃干燥24小时，去除水分；Step 1: Ultrasonically wash the biomass walnut catalpa wood chips with absolute ethanol for 12 hours to remove dust and impurities. The obtained product is dried in a blast drying oven at 30°C for 24 hours to remove moisture;
步骤二：将干燥后的胡桃楸木木屑转移至马弗炉中，在空气的气氛下以1℃/min的升温速率升温至200℃保温1小时，随炉自然冷却后取出，用粉碎机将预碳化产物粉碎至粉末状，备用；Step 2: Transfer the dried walnut and catalpa wood chips to a muffle furnace, heat them up to 200℃ at a heating rate of 1℃/min in an air atmosphere and keep them there for 1 hour. After natural cooling in the furnace, take them out and crush them with a pulverizer. The carbonized product is crushed to powder and set aside;
步骤三：将预碳化产物放入管式炉中，在惰性气体氮气的保护下，以0.25℃/min的升温速率由室温25℃升温至1300℃，保温2小时，随炉以5℃/min的降温速率冷却至室温，取出后研磨，并用325目的筛子进行过筛处理；Step 3: Put the pre-carbonized product into a tube furnace, and under the protection of inert gas nitrogen, heat it up from room temperature 25°C to 1300°C at a heating rate of 0.25°C/min, keep it warm for 2 hours, and continue with the furnace at 5°C/min. Cool to room temperature at a cooling rate, take it out, grind it, and sieve it through a 325-mesh sieve;
步骤四：将得到的粉末进行酸洗处理，所选的酸洗溶液为1M的稀硝酸溶液，浸泡24小时后用去离子水和乙醇反复离心洗涤至中性，将得到的产物在鼓风干燥箱中80℃干燥12小时，烘干后得到硬碳负极材料。Step 4: Pickle the obtained powder. The selected pickling solution is 1M dilute nitric acid solution. After soaking for 24 hours, repeatedly centrifuge and wash with deionized water and ethanol until neutral, and dry the obtained product in air. Dry in the box at 80°C for 12 hours, and obtain the hard carbon negative electrode material after drying.
实施例7Example 7
步骤一：将生物质核桃木木屑用丙酮洗涤8小时，去除灰尘杂质，得到的产物在鼓风干燥箱中80℃干燥24小时，去除水分；Step 1: Wash the biomass walnut wood chips with acetone for 8 hours to remove dust and impurities. The obtained product is dried in a blast drying oven at 80°C for 24 hours to remove moisture;
步骤二：将干燥后的核桃木木屑转移至马弗炉中，在空气的气氛下以20℃/min的升温速率升温至400℃保温5小时，随炉自然冷却后取出，用粉碎机将预碳化产物粉碎至粉末状，备用；Step 2: Transfer the dried walnut wood chips to the muffle furnace, heat it to 400℃ at a heating rate of 20℃/min in an air atmosphere and keep it there for 5 hours. After cooling naturally in the furnace, take it out and grind it with a pulverizer. The carbonized product is crushed to powder and set aside;
步骤三：将预碳化产物放入管式炉中，在氢氩混合气（5% H2+95% Ar）的保护下，以0.25℃/min的升温速率由室温25℃升温至1300℃，保温2小时，随炉以5℃/min的降温速率冷却至室温，取出后研磨，并用325目的筛子进行过筛处理；Step 3: Put the pre-carbonized product into a tube furnace, and under the protection of a hydrogen-argon mixture (5% H 2 + 95% Ar), heat it from room temperature 25°C to 1300°C at a heating rate of 0.25°C/min. Keep it warm for 2 hours, then cool to room temperature in the furnace at a cooling rate of 5°C/min, take it out, grind it, and sieve it with a 325-mesh sieve;
步骤四：将得到的粉末进行酸洗处理，所选的酸洗溶液为5M的乙酸溶液，浸泡1小时后用去离子水和乙醇反复离心洗涤至中性，将得到的产物在鼓风干燥箱中80℃干燥12小时，烘干后得到硬碳负极材料。Step 4: Pickle the obtained powder. The selected pickling solution is 5M acetic acid solution. After soaking for 1 hour, use deionized water and ethanol to repeatedly centrifuge and wash until neutral. Put the obtained product in a blast drying oven. Dry at 80°C for 12 hours, and obtain the hard carbon negative electrode material after drying.
实施例8Example 8
步骤一：将生物质榆木木屑用去离子水洗涤8小时，去除灰尘杂质，得到的产物在鼓风干燥箱中60℃干燥24小时，去除水分；Step 1: Wash the biomass elm wood chips with deionized water for 8 hours to remove dust and impurities. The obtained product is dried in a blast drying oven at 60°C for 24 hours to remove moisture;
步骤二：将干燥后的榆木木屑转移至马弗炉中，在空气的气氛下以15℃/min的升温速率升温至350℃保温5小时，随炉自然冷却后取出，用粉碎机将预碳化产物粉碎至粉末状，备用；Step 2: Transfer the dried elm wood chips to the muffle furnace, heat it to 350℃ at a heating rate of 15℃/min in an air atmosphere and keep it for 5 hours. After cooling naturally in the furnace, take it out and grind it with a pulverizer. The carbonized product is crushed to powder and set aside;
步骤三：将预碳化产物放入管式炉中，在氮气的保护下，以0.5℃/min的升温速率由室温25℃升温至1300℃，保温2小时，随炉以5℃/min的降温速率冷却至室温，取出后研磨，并用325目的筛子进行过筛处理；Step 3: Put the pre-carbonized product into a tube furnace, under the protection of nitrogen, heat it from room temperature 25°C to 1300°C at a heating rate of 0.5°C/min, keep it warm for 2 hours, and then cool down the furnace at a rate of 5°C/min. Cool to room temperature, take out, grind, and sieve through a 325-mesh sieve;
步骤四：将得到的粉末进行酸洗处理，所选的酸洗溶液为1M硫酸的溶液，浸泡3小时后用去离子水和乙醇反复离心洗涤至中性，将得到的产物在鼓风干燥箱中80℃干燥12小时，烘干后得到硬碳负极材料。Step 4: Pickle the obtained powder. The selected pickling solution is a 1M sulfuric acid solution. After soaking for 3 hours, use deionized water and ethanol to repeatedly centrifuge and wash until neutral. Put the obtained product in a blast drying oven. Dry at 80°C for 12 hours, and obtain the hard carbon negative electrode material after drying.
实施例9Example 9
步骤一：将生物质苦楝木木屑用无水乙醇洗涤4小时，去除灰尘杂质，得到的产物在鼓风干燥箱中80℃干燥24小时，去除水分；Step 1: Wash the biomass neem wood chips with absolute ethanol for 4 hours to remove dust and impurities. The obtained product is dried in a blast drying oven at 80°C for 24 hours to remove moisture;
步骤二：将干燥后的苦楝木木屑转移至马弗炉中，在空气的气氛下以10℃/min的升温速率升温至300℃保温2小时，随炉自然冷却后取出，用粉碎机将预碳化产物粉碎至粉末状，备用；Step 2: Transfer the dried neem wood chips to a muffle furnace, heat it to 300℃ at a heating rate of 10℃/min in an air atmosphere and keep it there for 2 hours. After cooling naturally in the furnace, take it out and grind it with a pulverizer. The carbonized product is crushed to powder and set aside;
步骤三：将预碳化产物放入管式炉中，在氩气的保护下，以1℃/min的升温速率由室温25℃升温至1300℃，保温2小时，随炉以5℃/min的降温速率冷却至室温，取出后研磨，并用325目的筛子进行过筛处理；Step 3: Put the pre-carbonized product into the tube furnace, under the protection of argon gas, heat it from room temperature 25°C to 1300°C at a heating rate of 1°C/min, keep it warm for 2 hours, and then heat it up with the furnace at a temperature of 5°C/min. Cool down to room temperature, take it out, grind it, and sieve it through a 325-mesh sieve;
步骤四：将得到的粉末进行酸洗处理，所选的酸洗溶液为2M的硝酸溶液，浸泡3小时后用去离子水和乙醇反复离心洗涤至中性，将得到的产物在鼓风干燥箱中80℃干燥12小时，烘干后得到硬碳负极材料。Step 4: Pickle the obtained powder. The selected pickling solution is 2M nitric acid solution. After soaking for 3 hours, use deionized water and ethanol to repeatedly centrifuge and wash until neutral. Put the obtained product in a blast drying oven. Dry at 80°C for 12 hours, and obtain the hard carbon negative electrode material after drying.
对比例1Comparative example 1
对比实施例4，对比例1提供了一种高升温速率为5℃/min的硬碳材料的制备方法。Comparative Example 4, Comparative Example 1 provides a method for preparing hard carbon materials with a high heating rate of 5°C/min.
步骤一：将生物质樟木木屑用去离子水超声洗涤6小时，去除灰尘杂质，得到的产物在鼓风干燥箱中60℃干燥24小时，去除水分；Step 1: Ultrasonically wash the biomass camphor wood chips with deionized water for 6 hours to remove dust and impurities. The obtained product is dried in a blast drying oven at 60°C for 24 hours to remove moisture;
步骤二：将干燥后的樟木木屑转移至马弗炉中，在空气的气氛下以3℃/min的升温速率升温至300℃保温2小时，随炉自然冷却后取出，用粉碎机将预碳化产物粉碎至粉末状，备用；Step 2: Transfer the dried camphor wood chips to the muffle furnace, heat it to 300℃ at a heating rate of 3℃/min in an air atmosphere and keep it for 2 hours. After natural cooling in the furnace, take it out and crush it with a pulverizer. The carbonized product is crushed to powder and set aside;
步骤三：将预碳化产物放入管式炉中，在惰性气体氩气的保护下，以5℃/min的升温速率由室温25℃升温至1300℃，保温2小时，随炉以5℃/min的降温速率冷却至室温，取出后研磨，并用325目的筛子进行过筛处理；Step 3: Put the pre-carbonized product into a tube furnace, and under the protection of inert gas argon, heat it from room temperature 25°C to 1300°C at a heating rate of 5°C/min, keep it warm for 2 hours, and then heat it up with the furnace at 5°C/min. Cool to room temperature at a cooling rate of min, take it out, grind it, and sieve it with a 325-mesh sieve;
步骤四：将得到的粉末进行酸洗处理，所选的酸洗溶液为2 M的稀盐酸溶液，浸泡12小时后用去离子水和乙醇反复离心洗涤至中性，将得到的产物在鼓风干燥箱中80℃干燥12小时，烘干后得到硬碳负极材料。Step 4: The obtained powder is pickled. The selected pickling solution is 2 M dilute hydrochloric acid solution. After soaking for 12 hours, it is washed with deionized water and ethanol by repeated centrifugation until neutral. The obtained product is washed in air blast. Dry in a drying oven at 80°C for 12 hours, and obtain the hard carbon negative electrode material after drying.
对比例2Comparative example 2
对比实施例4，对比例2提供了一种高升温速率为2℃/min的硬碳材料的制备方法。Comparative Example 4, Comparative Example 2 provides a method for preparing hard carbon materials with a high heating rate of 2°C/min.
步骤一：将生物质樟木木屑用去离子水超声洗涤6小时，去除灰尘杂质，得到的产物在鼓风干燥箱中60℃干燥24小时，去除水分；Step 1: Ultrasonically wash the biomass camphor wood chips with deionized water for 6 hours to remove dust and impurities. The obtained product is dried in a blast drying oven at 60°C for 24 hours to remove moisture;
步骤二：将干燥后的樟木木屑转移至马弗炉中，在空气的气氛下以3℃/min的升温速率升温至300℃保温2小时，随炉自然冷却后取出，用粉碎机将预碳化产物粉碎至粉末状，备用；Step 2: Transfer the dried camphor wood chips to the muffle furnace, heat it to 300℃ at a heating rate of 3℃/min in an air atmosphere and keep it for 2 hours. After natural cooling in the furnace, take it out and crush it with a pulverizer. The carbonized product is crushed to powder and set aside;
步骤三：将预碳化产物放入管式炉中，在惰性气体氩气的保护下，以2℃/min的升温速率由室温25℃升温至1300℃，保温2小时，随炉以5℃/min的降温速率冷却至室温，取出后研磨，并用325目的筛子进行过筛处理；Step 3: Put the pre-carbonized product into a tube furnace, and under the protection of inert gas argon, heat it from room temperature 25°C to 1300°C at a heating rate of 2°C/min, keep it warm for 2 hours, and then heat the furnace at 5°C/min. Cool to room temperature at a cooling rate of min, take it out, grind it, and sieve it with a 325-mesh sieve;
步骤四：将得到的粉末进行酸洗处理，所选的酸洗溶液为2M的稀盐酸溶液，浸泡12小时后用去离子水和乙醇反复离心洗涤至中性，将得到的产物在鼓风干燥箱中80℃干燥12小时，烘干后得到硬碳负极材料。Step 4: Pickle the obtained powder. The selected pickling solution is 2M dilute hydrochloric acid solution. After soaking for 12 hours, use deionized water and ethanol to repeatedly centrifuge and wash until neutral. Dry the obtained product in air. Dry in the box at 80°C for 12 hours, and obtain the hard carbon negative electrode material after drying.
本发明一典型的实施方式提供一种硬碳材料电极片，将各个实施例和对比例得到的樟木碎屑硬碳钠离子电池负极材料与乙炔黑、羧甲基纤维素钠（CMC）和聚丙烯酸(PAA)按照质量比8:1:0.5:0.5的比例研磨均匀，加入适量去离子水磁力搅拌12小时得到混合均匀的电极浆料，用涂布机均匀涂在铜箔上，放置真空干燥箱中80℃真空干燥12小时，之后用冲片机将其制备成直径为12mm的圆片电极，得到硬碳材料电极片。A typical embodiment of the present invention provides a hard carbon material electrode sheet, which combines the camphor wood chip hard carbon sodium ion battery negative electrode material obtained in each embodiment and comparative example with acetylene black, sodium carboxymethylcellulose (CMC) and Grind the polyacrylic acid (PAA) evenly according to the mass ratio of 8:1:0.5:0.5. Add an appropriate amount of deionized water and magnetically stir for 12 hours to obtain a uniformly mixed electrode slurry. Use a coater to evenly coat the copper foil and place it under vacuum. Vacuum dry at 80°C for 12 hours in a drying box, and then use a punching machine to prepare a disc electrode with a diameter of 12 mm to obtain a hard carbon material electrode sheet.
本实施例提供一种钠离子电池半电池，将上述所得电极片作为负极，将所述硬碳材料电极片裁剪得到直径为12 mm的圆片，用压片机压实，在高纯氩气填充的手套箱中按照CR2016标准扣式电池的构造组装电池，其中直径为19 mm的玻璃纤维(Whitman, GF/A)圆片作为隔膜，直径12 mm厚度0.2 mm的钠金属片作为对电极和参比电极，1 mol/L高氯酸钠/碳酸乙烯酯/碳酸二甲酯溶液作为电解液，静置12 h后在蓝电电池测试平台上用20 mA/g的电流密度对电池进行充放电测试。This embodiment provides a sodium-ion battery half-cell. The electrode sheet obtained above is used as a negative electrode. The hard carbon material electrode sheet is cut into a disc with a diameter of 12 mm, which is compacted with a tablet press and placed in high-purity argon gas. The battery was assembled in the filled glove box according to the CR2016 standard button cell structure, in which a glass fiber (Whitman, GF/A) disc with a diameter of 19 mm was used as the separator, a sodium metal sheet with a diameter of 12 mm and a thickness of 0.2 mm was used as the counter electrode and Reference electrode, 1 mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution was used as the electrolyte. After standing for 12 hours, the battery was charged on the blue battery test platform with a current density of 20 mA/g. Discharge test.
表1 实施例1-5和对比例1-2的主要参数及储钠性能Table 1 Main parameters and sodium storage performance of Examples 1-5 and Comparative Examples 1-2
图1所示的XRD图可以看出实施例1,2,4和对比例1,2的五种样品均在24°和43° (2θ )处出现2个弱而宽的衍射峰，分别对应于( 002 )和( 100 )晶面的衍射，随着升温速率的降低，( 002 )峰向更低的衍射角偏移，2θ从24.42°偏移到23.48°，计算得到平均层间距d002分别为0.364、0.367、 0.371、0.374和0.378 nm，其中实施例4所制备的硬碳材料具有较大的层间距，有利于钠离子的嵌入和脱出。From the XRD pattern shown in Figure 1, it can be seen that the five samples of Examples 1, 2, 4 and Comparative Examples 1 and 2 all have two weak and broad diffraction peaks at 24° and 43° (2θ), corresponding to Diffraction on (002) and (100) crystal planes, as the heating rate decreases, the (002) peak shifts to a lower diffraction angle, 2θ shifts from 24.42° to 23.48°, and the average layer spacing d002 is calculated respectively are 0.364, 0.367, 0.371, 0.374 and 0.378 nm. The hard carbon material prepared in Example 4 has a larger interlayer spacing, which is beneficial to the insertion and extraction of sodium ions.
图2所示的拉曼光谱可以看出实施例1,2,4和对比例1,2的五种样品分别在~ 1340cm-1和~ 1590 cm-1处显示两个宽峰，分别代表D峰和G峰，一般用D峰和G峰的积分面积强度比来表征碳材料的石墨化程度。随着升温速率的降低，ID / IG值不断下降，从1.63下降到1.48，其中实施例4所制备的硬碳材料具有较高的石墨化程度。From the Raman spectra shown in Figure 2, it can be seen that the five samples of Examples 1, 2, 4 and Comparative Examples 1 and 2 show two broad peaks at ~1340cm -1 and ~1590cm -1 respectively, representing D respectively. Peak and G peak, the integrated area intensity ratio of D peak and G peak is generally used to characterize the degree of graphitization of carbon materials. As the heating rate decreases, the I D / I G value continues to decrease, from 1.63 to 1.48, in which the hard carbon material prepared in Example 4 has a higher degree of graphitization.
图3所示的充放电曲线图可以看出对比例1的材料在电流密度为20 mA/g和电压区间为0-2V，其显示出67.5%的首次库伦效率和242.6mAh/g的初始比容量，具有明显的充放电平台。The charge-discharge curve shown in Figure 3 shows that the material of Comparative Example 1 shows a first Coulombic efficiency of 67.5% and an initial ratio of 242.6mAh/g at a current density of 20 mA/g and a voltage range of 0-2V. capacity, with an obvious charging and discharging platform.
图4所示的充放电曲线图可以看出实施例4的材料在电流密度为20 mA/g和电压区间为0-2V，其显示出较高的首次库伦效率（82.8%）和初始比容量（324.6mAh/g），具有较高的平台容量占比。From the charge and discharge curve shown in Figure 4, it can be seen that the material of Example 4 shows high first Coulombic efficiency (82.8%) and initial specific capacity at a current density of 20 mA/g and a voltage range of 0-2V. (324.6mAh/g), with a high platform capacity ratio.
图5所示的循环性能图可以看出实施例1,2,4和对比例1,2的五种硬碳材料都显示出良好循环稳定性，其中实施例5所制备的硬碳材料具有最高的可逆比容量，在20mA/g的电流密度下循环50次后仍具有98.4%的高容量保持率。The cycle performance chart shown in Figure 5 shows that the five hard carbon materials of Examples 1, 2, 4 and Comparative Examples 1, 2 all show good cycle stability, among which the hard carbon material prepared in Example 5 has the highest The reversible specific capacity still has a high capacity retention rate of 98.4% after 50 cycles at a current density of 20mA/g.
图6所示的SEM图可以看出实施例4的硬碳材料显示出分层多孔结构，有利于钠离子的嵌入和脱出，其表面显示出较少的微孔，可减少不可逆容量的损失。The SEM image shown in Figure 6 shows that the hard carbon material of Example 4 exhibits a hierarchical porous structure, which is conducive to the insertion and extraction of sodium ions, and its surface exhibits fewer micropores, which can reduce irreversible capacity loss.
图7所示的HRTEM图可以看出实施例4的硬碳材料显示出典型的无定形结构并具有大量短程有序石墨层，其层间距为0.379 nm。From the HRTEM image shown in Figure 7, it can be seen that the hard carbon material of Example 4 shows a typical amorphous structure and has a large number of short-range ordered graphite layers, and the interlayer spacing is 0.379 nm.
如表1所示，通过对比实施例3,4,5可以看出，通过对硬碳材料进行热解温度的改变，材料随着温度的升高，可逆比容量呈现先增加后减少的趋势，1300℃为最佳的碳化温度；通过对比实施例1,2,4和对比例1,2可以看出，通过降低材料在热解过程中的升温速率，材料的首次库伦效率从67.5%提高至82.8%，初始比容量从242.6mAh/g提高至324.6mAh/g；通过降低碳化过程中的升温速率，降低材料的缺陷浓度，提高材料的层间距和石墨化程度，可以有效提高材料的首次库伦效率和可以比容量，改善材料的储钠性能。As shown in Table 1, by comparing Examples 3, 4, and 5, it can be seen that by changing the pyrolysis temperature of the hard carbon material, as the temperature of the material increases, the reversible specific capacity shows a trend of first increasing and then decreasing. 1300°C is the optimal carbonization temperature; by comparing Examples 1, 2, 4 and Comparative Examples 1, 2, it can be seen that by reducing the heating rate of the material during the pyrolysis process, the first Coulombic efficiency of the material is increased from 67.5% to 82.8%, the initial specific capacity increased from 242.6mAh/g to 324.6mAh/g; by reducing the temperature rise rate during the carbonization process, reducing the defect concentration of the material, increasing the layer spacing and graphitization degree of the material, the first Coulomb of the material can be effectively improved efficiency and specific capacity, improving the sodium storage performance of the material.
以上所述实施例1-9仅为本发明的较佳实施例，描述了本发明的基本原理和特征，本发明并不局限于上述的具体实施方式，凡在本发明所公示的方法之内所作的改进和优化等，均属于本发明的保护之内。The above-mentioned Embodiments 1-9 are only preferred embodiments of the present invention, describing the basic principles and characteristics of the present invention. The present invention is not limited to the above-mentioned specific implementations. All methods disclosed in the present invention are The improvements and optimizations made are within the protection of the present invention.
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