CN117293303A - 一种锂硫电池负极材料及其制备方法和应用 - Google Patents
一种锂硫电池负极材料及其制备方法和应用 Download PDFInfo
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- CN117293303A CN117293303A CN202311578150.6A CN202311578150A CN117293303A CN 117293303 A CN117293303 A CN 117293303A CN 202311578150 A CN202311578150 A CN 202311578150A CN 117293303 A CN117293303 A CN 117293303A
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000010405 anode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 66
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 35
- 239000010941 cobalt Substances 0.000 claims abstract description 35
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 35
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011787 zinc oxide Substances 0.000 claims abstract description 23
- 239000002135 nanosheet Substances 0.000 claims abstract description 18
- 239000007773 negative electrode material Substances 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims description 37
- 150000003751 zinc Chemical class 0.000 claims description 30
- 238000010041 electrostatic spinning Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 24
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 19
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000010335 hydrothermal treatment Methods 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001523 electrospinning Methods 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- CODVACFVSVNQPY-UHFFFAOYSA-N [Co].[C] Chemical compound [Co].[C] CODVACFVSVNQPY-UHFFFAOYSA-N 0.000 claims description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 28
- 230000006911 nucleation Effects 0.000 abstract description 5
- 238000010899 nucleation Methods 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 8
- 210000001787 dendrite Anatomy 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000010000 carbonizing Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
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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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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
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- H—ELECTRICITY
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Abstract
本发明公开了一种锂硫电池负极材料及其制备方法和应用,属于锂硫电池负极材料的制备技术领域。锂硫电池负极材料包括掺铝氧化锌纳米片包裹的负载单质钴的碳纳米纤维,其中所述掺铝氧化锌纳米片与碳纳米纤维的质量比为0.30~0.44:1,钴负载量为碳纳米纤维质量的23.8~39.5%。本发明制备的掺铝氧化锌纳米片能够负载更多的锂,有效改善负极材料体积膨胀和收缩问题;铝的掺杂可提高氧化锌导电性,有效降低局部电流密度,使锂的成核和生长更加均匀;碳纳米纤维为单质钴的分散提供了缓冲空间,单质钴可有效调节局部电子结构,增强对Li+的吸附。采用本发明的锂硫电池负极材料用于锂硫电池中,有效提高了电池的容量和循环性能。
Description
技术领域
本发明属于锂硫电池负极材料的制备技术领域,具体涉及一种锂硫电池负极材料及其制备方法和应用。
背景技术
随着对便携式电子设备、电动汽车以及电网储能的需求不断增长,人们迫切需要开发出超越锂离子电池的新型储能系统。锂硫电池因其高理论比容量(Li:3860mAh/g,S:1675mAh/g)和低质量密度(Li:0.534g/cm3,S:2.07g/cm3)等优点成为下一代最有潜力的储能系统之一。然而,锂硫电池的实际应用仍然受到严重阻碍。首先,锂枝晶的生长可能穿透隔膜,导致内部短路。其次,剥离/电镀过程中体积会显著变化,导致电极极化和接触不稳定等严重问题。同时,锂负极的体积变化通常与固体电解质界面的持续形成和断裂有关,这可能导致锂枝晶不断消耗电解液,从而降低锂硫电池的循环寿命和库仑效率。
为了突破这些瓶颈,人们采用多种策略来改善锂负极,包括制造人工固体电解质界面层、添加新的电解质添加剂、研发固态或聚合物电解质、以及设计多孔导电基底(如三维泡沫铜和泡沫镍)作为锂载体等方法。特别是,多孔导电基底作为锂载体具有一定的优势。多孔导电基底可以在连续电镀/剥离过程中同时缓解锂枝晶生长并最大限度地减少体积变化。然而,这些金属基底的高质量密度大大降低了负极的能量密度和功率密度。因此,探索轻质、多孔、亲锂的宿主材料是非常可取的。公开号为CN113130881A的中国专利文件,公开了一种锂硫电池负极材料的制备方法。该制备方法所得的负极材料具有大的比表面积,可以提供更多的沉积位,诱导锂沉积的形成。然而,三维框架由于对Li+的吸附能力较差,所以很难有效调节电极/电解质界面附近的Li+浓度。鉴于此,选择合适的亲锂物种能够显著降低锂成核过电位,并促进锂的均匀沉积。
发明内容
本发明的目的在于,提供一种锂硫电池负极材料及其制备方法和应用,可以解决制备负极过程中添加导电剂、粘结剂和集流体导致成本升高、能量密度降低等问题并且促进锂的均匀沉积,有效抑制锂枝晶生长的问题。所提供的锂硫电池负极材料显著提高了锂硫电池的电化学的稳定性,表现出优异的比容量、库仑效率和循环稳定性。
为了实现上述发明目的,本发明提供的锂硫电池负极材料包括掺铝氧化锌纳米片包裹的负载单质钴的碳纳米纤维,其中所述掺铝氧化锌纳米片与碳纳米纤维的质量比为0.30~0.44:1,钴负载量为碳纳米纤维质量的23.8~39.5%。
本发明提供的一种锂硫电池负极材料的制备方法,包括如下步骤:
(1)在N,N-二甲基甲酰胺中依次加入碳源、钴源和造孔剂,制得静电纺丝溶液,所述的碳源为聚丙烯腈、聚乙烯吡咯烷酮中的至少一种,钴源为乙酸钴、硝酸钴和草酸钴中的一种,造孔剂为聚甲基丙烯酸甲酯、聚苯乙烯中的至少一种,碳源、钴源和造孔剂的质量比为0.8~2.5:1:0.2~0.8;
(2)静电纺丝溶液经静电纺丝制得纤维膜;
(3)将纤维膜置于保护气氛和500~900℃温度下煅烧,制得负载单质钴的碳纳米纤维;
(4)将铝盐、锌盐、氟化铵与尿素混合溶于水或乙醇,得到前驱体溶液;其中,锌盐在前驱体溶液的摩尔浓度为0.01~0.1mol/L,铝盐与锌盐的摩尔比为1~5:100,氟化铵与锌盐的摩尔比为1~5:1,尿素与锌盐的摩尔比为1~10:1;
(5)将负载单质钴的碳纳米纤维放入前驱体溶液中进行水热处理,取出处理后的碳纳米纤维,经水或乙醇洗涤并干燥,得到前体;
(6)在保护气氛和温度200~800℃下,将前体进行煅烧,得到掺铝氧化锌纳米片包裹的负载单质钴碳纳米纤维材料,即为锂硫电池负极材料。
优选地,步骤(2)中,静电纺丝的工艺参数为:负高压为-3~-1kV,正高压为10~20kV,静电纺丝溶液推速为0.1~0.8ml/min,收集器转速为50~100r/min,接收距离为10~20cm。
优选地,步骤(3)中,保护气氛为氮气或氩气,升温速率为2~4℃/min,煅烧时间为6~8h。
优选地,步骤(4)中,铝盐为氯化铝或硝酸铝;所述的锌盐为乙酸锌或硝酸锌;锌盐在前驱体溶液的摩尔浓度为0.05~0.95mol/L,铝盐与锌盐的摩尔比为1~3:100,氟化铵与锌盐的摩尔比为2~4:1,尿素与锌盐的摩尔比为3~6:1。
优选地,步骤(5)中,水热处理温度为120~200℃,时间为6~10h;干燥温度为60~80℃,时间为4~8h。
优选地,步骤(6)中,保护气氛为氮气或氩气,升温速率为2~5℃/min,煅烧时间为3~6h。
本发明所述的锂硫电池负极材料的应用,将锂硫电池负极材料用于锂硫电池的负极。
本发明的有益效果如下:1.本发明采用静电纺丝方法制备的碳纳米纤维具有以下优势:首先,碳纳米纤维为单质钴的分散提供了缓冲空间,防止其团聚,这有利于活性位点的充分暴露,进一步提高单质钴的利用率。此外,碳纳米纤维能够缓解电池在循环过程中的体积应变,有效降低局部电流密度,从而促使锂的均匀沉积。2.单质钴具有金属特性和优异的导电性,有利于电子传输,因此可进一步提高碳纳米纤维的导电性,从而降低锂成核过电势,实现锂的均匀电镀,并且单质钴可有效调节局部电子结构,增强对Li+的吸附。3.本发明方法制备的掺铝氧化锌纳米片具有较大的比表面积,能够负载更多的锂,有效改善负极材料体积膨胀和收缩问题;此外,铝的掺杂可提高氧化锌导电性,有效降低局部电流密度,使锂的成核和生长更加均匀。4.本发明制备的锂硫电池负极材料(AZO@Co-CNFs)应用于锂硫电池负极,作为锂的宿主材料,可以解决制备负极过程中添加导电剂、粘结剂和集流体导致成本升高、能量密度降低等问题并且促进锂的均匀沉积,从而有效抑制锂枝晶生长的问题。5.综上所述,通过本发明方法制备的AZO@Co-CNFs材料在锂硫电池负极应用中表现突出。在1C下,该锂硫电池的初始比容量高达946.1~951.8mAh/g,并在500次循环测试中容量衰减率低至每循环0.018%~0.020%。
附图说明
图1为实施例1制备的AZO@Co-CNFs材料的扫描电子显微镜(SEM)图;
图2为实施例1制备的AZO@Co-CNFs材料的X射线衍射(XRD)图;
图3为实施例1制备的AZO@Co-CNFs材料的Co 2pX射线光电子能谱(XPS)图;
图4为实施例1制备的AZO@Co-CNFs材料的拉曼(Raman)图;
图5为实施例1制备的AZO@Co-CNFs材料在1C下的循环稳定性;
具体实施方式
下面结合实施例与对比例来详细说明本发明,但本发明并不仅限于此。
实施例1
(1)在20mlN,N-二甲基甲酰胺中依次加入1g聚丙烯腈、1g聚乙烯吡咯烷酮、1g硝酸钴、0.2g聚甲基丙烯酸甲酯和0.4g聚苯乙烯,充分溶解后,得到静电纺丝溶液。其中碳源、钴源和造孔剂的质量比为2:1:0.6;
(2)将步骤(1)制备的静电纺丝溶液转移至医用注射器内,注射器针尖与收集器之间的距离为20cm,设置负高压和正高压分别为-2kV和10kV,静电纺丝溶液推速为0.5ml/min,收集器转速为80r/min,于此条件下静电纺丝,结束后制得纤维膜;
(3)将步骤(2)得到的纤维膜进行碳化,纤维膜置于氩气气氛下,以2℃/min的升温速率升至800℃,煅烧时间为6h,制得负载单质钴的碳纳米纤维(Co-CNFs);
(4)将硝酸铝、硝酸锌、氟化铵与尿素混合溶于水得到100ml前驱体溶液;其中,硝酸锌在前驱体溶液的摩尔浓度为0.05mol/L,硝酸铝与硝酸锌的摩尔比为1:100,氟化铵与锌盐的摩尔比为2:1,尿素与锌盐的摩尔比为4:1;
(5)将Co-CNFs放入前驱体溶液的反应釜中,在120℃的烘箱内水热处理6h,从反应釜中取出样品后,用水清洗,在60℃条件下的干燥箱中干燥4h,得到前体;
(6)将前体在氮气气氛下,以4℃/min的升温速率升至500℃并保温6h进行煅烧,得到掺铝氧化锌纳米片包裹的负载单质钴碳纳米纤维锂硫电池负极材料(AZO@Co-CNFs)。
本实施例得到的锂硫电池负极材料,通过电感耦合原子发射光谱(ICP-AES)测量掺铝氧化锌纳米片与碳纳米纤维的质量比为0.33:1,钴负载量为碳纳米纤维质量的25.7%。
实施例2
(1)在20mlN,N-二甲基甲酰胺中依次加入0.8g聚丙烯腈、1g草酸钴和0.8g聚甲基丙烯酸甲酯,充分溶解后,得到静电纺丝溶液。其中碳源、钴源和造孔剂的质量比为0.8:1:0.8;
(2)将步骤(1)制备的静电纺丝溶液转移至医用注射器内,注射器针尖与收集器之间的距离为10cm,设置负高压和正高压分别为-1kV和13kV,静电纺丝溶液推速为0.1ml/min,收集器转速为100r/min,于此条件下静电纺丝,结束后制得纤维膜;
(3)将步骤(2)得到的纤维膜进行碳化,纤维膜置于氮气气氛下,以3℃/min的升温速率升至600℃,煅烧时间为8h,制得Co-CNFs;
(4)将氯化铝、乙酸锌、氟化铵与尿素混合溶于水得到100ml前驱体溶液;其中,乙酸锌在前驱体溶液的摩尔浓度为0.01mol/L,氯化铝与乙酸锌的摩尔比为1:20,氟化铵与锌盐的摩尔比为1:1,尿素与锌盐的摩尔比为1:1;
(5)将Co-CNFs放入前驱体溶液的反应釜中,在200℃的烘箱内水热处理8h,从反应釜中取出样品后,用水清洗,在70℃条件下的干燥箱中干燥8h,得到前体;
(6)将前体在氩气气氛下,以2℃/min的升温速率升至200℃并保温3h进行煅烧,得到AZO@Co-CNFs。
本实施例得到的锂硫电池负极材料,通过ICP-AES测量掺铝氧化锌纳米片与碳纳米纤维的质量比为0.30:1,钴负载量为碳纳米纤维质量的36.5%。
实施例3
(1)在20mlN,N-二甲基甲酰胺中依次加入2.5g聚乙烯吡咯烷酮、1g乙酸钴和0.35g聚苯乙烯,充分溶解后,得到静电纺丝溶液。其中碳源、钴源和造孔剂的质量比为2.5:1:0.35;
(2)将步骤(1)制备的静电纺丝溶液转移至医用注射器内,注射器针尖与收集器之间的距离为12cm,设置负高压和正高压分别为-3kV和20kV,静电纺丝溶液推速为0.75ml/min,收集器转速为50r/min,于此条件下静电纺丝,结束后制得纤维膜;
(3)将步骤(2)得到的纤维膜进行碳化,纤维膜置于氮气气氛下,以4℃/min的升温速率升至500℃,煅烧时间为6.5h,制得Co-CNFs;
(4)将氯化铝、硝酸锌、氟化铵与尿素混合溶于乙醇得到100ml前驱体溶液;其中,硝酸锌在前驱体溶液的摩尔浓度为0.1mol/L,氯化铝与硝酸锌的摩尔比为3:100,氟化铵与锌盐的摩尔比为5:1,尿素与锌盐的摩尔比为10:1;
(5)将Co-CNFs放入前驱体溶液的反应釜中,在150℃的烘箱内水热处理9h,从反应釜中取出样品后,用乙醇清洗,在80℃条件下的干燥箱中干燥6h,得到前体;
(6)将前体在氮气气氛下,以5℃/min的升温速率升至800℃并保温4h进行煅烧,得到AZO@Co-CNFs。
本实施例得到的锂硫电池负极材料,通过ICP-AES测量掺铝氧化锌纳米片与碳纳米纤维的质量比为0.44:1,钴负载量为碳纳米纤维质量的23.8%。
实施例4
(1)在20mlN,N-二甲基甲酰胺中依次加入0.8g聚丙烯腈、0.4g聚乙烯吡咯烷酮、1g乙酸钴和0.2g聚甲基丙烯酸甲酯,充分溶解后,得到静电纺丝溶液。其中碳源、钴源和造孔剂的质量比为1.2:1:0.2;
(2)将步骤(1)制备的静电纺丝溶液转移至医用注射器内,注射器针尖与收集器之间的距离为20cm,设置负高压和正高压分别为-3kV和17kV,静电纺丝溶液推速为0.8ml/min,收集器转速为100r/min,于此条件下静电纺丝,结束后制得纤维膜;
(3)将步骤(2)得到的纤维膜进行碳化,纤维膜置于氩气气氛下,以3℃/min的升温速率升至900℃,煅烧时间为8h,制得Co-CNFs;
(4)将硝酸铝、乙酸锌、氟化铵与尿素混合溶于乙醇得到100ml前驱体溶液;其中,乙酸锌在前驱体溶液的摩尔浓度为0.095mol/L,硝酸铝与乙酸锌的摩尔比为1:50,氟化铵与锌盐的摩尔比为4:1,尿素与锌盐的摩尔比为3:1;
(5)将Co-CNFs放入前驱体溶液的反应釜中,在140℃的烘箱内水热处理10h,从反应釜中取出样品后,用乙醇清洗,在65℃条件下的干燥箱中干燥8h,得到前体;
(6)将前体在氩气气氛下,以3℃/min的升温速率升至300℃并保温3h进行煅烧,得到AZO@Co-CNFs。
本实施例得到的锂硫电池负极材料,通过ICP-AES测量得到掺铝氧化锌纳米片与碳纳米纤维的质量比为0.40:1,钴负载量为碳纳米纤维质量的39.5%。
实施例5
(1)在20mlN,N-二甲基甲酰胺中依次加入2.3g聚乙烯吡咯烷酮、1g硝酸钴、0.5g聚甲基丙烯酸甲酯和0.2g聚苯乙烯,充分溶解后,得到静电纺丝溶液。其中碳源、钴源和造孔剂的质量比为2.3:1:0.7;
(2)将步骤(1)制备的静电纺丝溶液转移至医用注射器内,注射器针尖与收集器之间的距离为10cm,设置负高压和正高压分别为-3kV和20kV,静电纺丝溶液推速为0.3ml/min,收集器转速为60r/min,于此条件下静电纺丝,结束后制得纤维膜;
(3)将步骤(2)得到的纤维膜进行碳化,纤维膜置于氮气气氛下,以2℃/min的升温速率升至700℃,煅烧时间为7.5h,制得Co-CNFs;
(4)将硝酸铝、硝酸锌、氟化铵与尿素混合溶于水得到100ml前驱体溶液;其中,硝酸锌在前驱体溶液的摩尔浓度为0.07mol/L,硝酸铝与硝酸锌的摩尔比为1:100,氟化铵与锌盐的摩尔比为3:1,尿素与锌盐的摩尔比为4:1;
(5)将Co-CNFs放入前驱体溶液的反应釜中,在180℃的烘箱内水热处理8h,从反应釜中取出样品后,用水清洗,在60℃条件下的干燥箱中干燥4h,得到前体;
(6)将前体在氮气气氛下,以5℃/min的升温速率升至600℃并保温6h进行煅烧,得到AZO@Co-CNFs。
本实施例得到的锂硫电池负极材料,通过ICP-AES测量掺铝氧化锌纳米片与碳纳米纤维的质量比为0.41:1,钴负载量为碳纳米纤维质量的24.6%。
对比例1
本对比例在制备静电纺丝溶液时不加钴源,其他均与实施例1的过程一致。
本实施例得到的锂硫电池负极材料,通过ICP-AES测量得到掺铝氧化锌纳米片与碳纳米纤维的质量比为34.6%。
对比例2
本对比例在制备前驱体溶液时不加铝源,其他均与实施例1的过程一致。
本实施例得到的锂硫电池负极材料,通过ICP-AES测量得到掺钴氧化锌纳米片与碳纳米纤维的质量比为0.33:1,钴负载量为碳纳米纤维质量的25.8%。
将上述实施例1-5和对比例1-2中得到的锂硫电池负极材料分别通过公知的电化学沉积方法载锂,载锂量控制为4mAh/cm2,得到载锂的负极。
将载硫的CNFs正极片(活性物质载量1.5mg/cm2)和载锂的负极在充满高纯氩气的手套箱中进行组装C2032纽扣电池,聚丙烯多孔膜(Celgard2300)为隔膜,电解液为1.0mol/L LiTFSI和0.2mol/LLiN03与1,3-二氧戊环和1,2-二甲氧基乙烷(w/w,1/1)的混合溶液。在CT-4008-5A6V系统上,以固定电位范围(1.7-2.8Vvs.Li+/Li)的不同电流密度下对电池进行循环测试。测试电流密度为0.2C/1C,其中1C等于1672mA/g,测试电压范围为1.7-2.8V。
图1为实施例1制备的AZO@Co-CNFs的SEM形貌图。从图1中可以看出,锂硫电池负极材料表面均匀包裹了掺铝氧化锌(AZO)纳米片结构,应用为锂硫电池负极能够为锂金属的分散提供缓冲空间,以确保锂金属的均匀生长/成核,有利于提高材料的性能表现。
通过XRD揭示AZO@Co-CNFs的晶体结构,结果如图2所示。实施例1样品的所有主要衍射峰显示出明显的ZnO六方晶体相(PDF#79-0206),同时Al元素的掺杂并没有改变ZnO的晶体结构,证明了Al元素的成功掺杂。图3显示了AZO@Co-CNFs的Co2p XPS光谱,可以观察到Co0态的特征峰,表明碳纳米纤维负载单质钴。图4展示了AZO@Co-CNFs的Raman光谱,1340cm-1处的特征峰可归因于无定形碳sp3缺陷的D波段,而1581cm-1处的特征峰可归因于石墨层平面内振动的G波段。
以实施例1制得的锂硫电池负极材料作为负极极片制备锂硫电池,对其进行电化学测试,其结果如图5所示。在1C的高电流密度下,其制备的锂硫电池具有优异的长期循环稳定性。其首次放电比容量为951.8mAh/g,库仑效率为99.7%,即使在500次循环后仍能保持866.2mAh/g,远远优于对比例1所制备的锂硫电池(698.8mAh/g)和对比例2所制备的锂硫电池(735.2mAh/g)(表1)。此外,实施例1所制备的锂硫电池容量衰减率低至每循环0.018%,这充分证明了AZO@Co-CNFs能有效抑制锂枝晶的生长,提高锂在长循环中的利用率。
对实施例2~5的材料进行相同的测试,结果和实施例1相近(表1),在1C电流密度下各实施例样品的首次放电比容量差值不超过6mAh/g,每圈容量衰减率差值不超过0.002%。
以上所述的具体实施方式,对本发明进行了进一步详细说明,不过这些说明并不能理解为对本发明的限制。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种锂硫电池负极材料,其特征在于,所述锂硫电池负极材料包括掺铝氧化锌纳米片包裹的负载单质钴的碳纳米纤维,其中所述掺铝氧化锌纳米片与碳纳米纤维的质量比为0.30~0.44:1,钴负载量为碳纳米纤维质量的23.8~39.5%。
2.一种锂硫电池负极材料的制备方法,其特征在于,包括如下步骤:
(1)在N,N-二甲基甲酰胺中依次加入碳源、钴源和造孔剂,制得静电纺丝溶液,所述的碳源为聚丙烯腈、聚乙烯吡咯烷酮中的至少一种,钴源为乙酸钴、硝酸钴和草酸钴中的一种,造孔剂为聚甲基丙烯酸甲酯、聚苯乙烯中的至少一种,碳源、钴源和造孔剂的质量比为0.8~2.5:1:0.2~0.8;
(2)静电纺丝溶液经静电纺丝制得纤维膜;
(3)将纤维膜置于保护气氛和500~900℃温度下煅烧,制得负载单质钴的碳纳米纤维;
(4)将铝盐、锌盐、氟化铵与尿素混合溶于水或乙醇,得到前驱体溶液;其中,锌盐在前驱体溶液的摩尔浓度为0.01~0.1mol/L,铝盐与锌盐的摩尔比为1~5:100,氟化铵与锌盐的摩尔比为1~5:1,尿素与锌盐的摩尔比为1~10:1;
(5)将负载单质钴的碳纳米纤维放入前驱体溶液中进行水热处理,取出处理后的碳纳米纤维,经水或乙醇洗涤并干燥,得到前体;
(6)在保护气氛和温度200~800℃下,将前体进行煅烧,得到掺铝氧化锌纳米片包裹的负载单质钴碳纳米纤维材料,即为锂硫电池负极材料。
3.根据权利要求2所述的锂硫电池负极材料的制备方法,其特征在于,所述的步骤(2)中,静电纺丝的工艺参数为:负高压为-3~-1kV,正高压为10~20kV,静电纺丝溶液推速为0.1~0.8ml/min,收集器转速为50~100r/min,接收距离为10~20cm。
4.根据权利要求2所述的锂硫电池负极材料的制备方法,其特征在于,所述的步骤(3)中,保护气氛为氮气或氩气,升温速率为2~4℃/min,煅烧时间为6~8h。
5.根据权利要求2所述的锂硫电池负极材料的制备方法,其特征在于,所述的步骤(4)中,铝盐为氯化铝或硝酸铝;所述的锌盐为乙酸锌或硝酸锌;锌盐在前驱体溶液的摩尔浓度为0.05~0.095mol/L,铝盐与锌盐的摩尔比为1~3:100,氟化铵与锌盐的摩尔比为2~4:1,尿素与锌盐的摩尔比为3~6:1。
6.根据权利要求2所述的锂硫电池负极材料的制备方法,其特征在于,所述的步骤(5)中,水热处理温度为120~200℃,时间为6~10h;干燥温度为60~80℃,时间为4~8h。
7.根据权利要求2所述的锂硫电池负极材料的制备方法,其特征在于,所述的步骤(6)中,保护气氛为氮气或氩气,升温速率为2~5℃/min,煅烧时间为3~6h。
8.一种如权利要求1所述的锂硫电池负极材料的应用,其特征在于,将所述的锂硫电池负极材料用于锂硫电池的负极。
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