CN112978700A - 一种锂离子电池负极材料偏磷酸钒氧及其制备方法与应用 - Google Patents
一种锂离子电池负极材料偏磷酸钒氧及其制备方法与应用 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000007773 negative electrode material Substances 0.000 title claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000084 colloidal system Substances 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 17
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000013067 intermediate product Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 239000010405 anode material Substances 0.000 claims abstract description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 3
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 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
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims 1
- 235000014633 carbohydrates Nutrition 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 6
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- 239000002245 particle Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 239000012071 phase Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910003206 NH4VO3 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 125000005341 metaphosphate group Chemical group 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
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- 238000009776 industrial production Methods 0.000 description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910017677 NH4H2 Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
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- 229910052987 metal hydride Inorganic materials 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- -1 nickel metal hydride Chemical class 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/44—Metaphosphates
-
- 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
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
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Abstract
本发明公开了一种锂离子电池负极材料偏磷酸钒氧及其制备方法与应用,该方法包括:将磷源和钒源溶于蒸馏水中,保持温度在60‑80℃范围内加热搅拌得到胶体,烘干得到干胶体;研磨,在空气气氛下300‑450℃热处理5‑6h,随炉冷却后研磨得到粉末状中间产物;在空气中550‑750℃烧结处理10‑24h,自然冷却后得到偏磷酸钒氧负极材料。本发明还包括再加入含碳材料,在惰性气氛中300‑600℃下再次烧结退火,得到碳包覆的偏磷酸钒氧。该方法工艺简单,操作容易,并且碳包覆不会使钒的价态(+4)价发生改变;制备的材料颗粒均一,结构稳定,表现出优异的电化学性能。该发明适用于生产高性能锂离子电池负极材料偏磷酸钒氧。
Description
技术领域
本发明属于锂离子电池负极材料技术领域,具体涉及一种锂离子电池负极材料偏磷酸钒氧及其制备方法与应用。
背景技术
20世纪70年代的石油危机促使研究人员寻找一种优越的电池系统来替代石油,此外,世界各国政府更加意识到温室气体对生态环境的破坏,并推出了许多关于绿色能源技术(太阳能、风能等)的解决方案。然而,太阳能和风能的间歇性意味着要想让这些可再生资源发挥作用,就需要先储存这些能量。因此,人们希望有更好的可充电电池。而镍金属氢化物和铅酸体系能量密度较低,未来发展潜力有限。为了寻找更高的能量密度体系,研究人员关注到有机电解质的宽电压窗口、锂的高还原性(-3.04V与标准氢电极对比)和低原子质量的特点。此外,锂离子的原子半径小,作为载流子具有较高的扩散系数。理论上是一种很有前景的便携式储能系统。于是最先出现了使用锂负极和有机液体电解质的不可充电电池,随后,人们致力于将锂离子插入过渡金属层状硫化物正极,以制造可充电电池。StanleyWhittingham制造了以层状TiS2为正极,通过可逆的锂插入放电形成LiTiS2的可充电电池,并于1976年报道了该电池的良好初始性能。1980年Armand提出“摇摆电池”的构想,采用低插锂电位的层间化合物代替金属锂作为负极,以高插锂点位的嵌锂化合物作为正极,组成没有锂金属的二次电池。
自从1991年索尼公司将世界上第一个锂离子电池商业化,锂离子电池具有能量密度高、倍率性能好、循环寿命长、电池工作温度范围宽、自放电率小等优点,其对便携式电子产品的革新,导致了随后几年研究的爆发性增长。多年来锂离子电池研究取得了巨大发展,已广泛应用于便携式电子产品、小型电器领域。然而,目前商业化锂离子电池大多以石墨作为负极,因为其嵌锂电位低(~0.1V),充放电过程中容易造成锂金属在负极表面的沉积,形成锂枝晶,刺穿隔膜引起内部短路,导致电池起火或爆炸,这一点在高功率电池上表现尤为明显,成为了制约锂离子电池在电动汽车(EV)或混合动力汽车(HEV)方面进一步发展和运用的关键性因素。因此,追求低成本、高能量密度、良好循环性能和安全可靠的新型负极材料代替石墨,以满足对锂离子电池日益增长的性能需求,是目前研究目标之一。
含有磷酸根的一系列材料,如磷酸盐、磷酸氢化合物、焦磷酸盐、混合磷酸盐等作为聚阴离子化合物,由于其结构稳定性强、锂离子扩散快、热稳定性好、制备方便、成本低廉等优点,作为电极材料得到了广泛的研究。但该类材料的电子和离子电导率较低,不适合在大电流密度下放电,因此可通过掺杂和碳包覆等手段进行改性。此外,位于VB族的钒元素可以进行从V2+到V5+的多价电化学反应,因此含有钒基团的化合物通常具有较高的理论容量。偏磷酸钒氧[VO(PO3)2]作为一类聚阴离子型化合物,具有成为锂离子电池高性能负极材料的潜力,目前未见其溶胶凝胶法合成的相关专利。
现有偏磷酸钒氧[VO(PO3)2]的合成方法可大致分为如下两类:第一,熔盐法或化学气相传输法等传统生长单晶的方法,该法中不仅需要加入高粘度助熔剂或运输剂等添加剂,需要特殊的双区炉仪器且对温度和气压等实验条件要求十分严格。第二,将磷酸与五氧化二钒混合于水或有机溶剂中,加入适当的还原剂并不断加热搅拌回流,还原五价钒;所得产物用丙酮等有机溶剂洗涤,待干燥后烧结。该法步骤繁琐,加热回流耗时较长且大量磷酸及有机溶剂丙酮的使用会造成环境污染。综合上述,偏磷酸钒氧[VO(PO3)2]现有的合成方法均具有成本较高、合成步骤繁琐且对实验条件要求高、对环境污染较大、不适合大规模工业化生产等缺点。
发明内容
本发明的目的在于提供一种锂离子电池负极材料偏磷酸钒氧[VO(PO3)2],并提供该材料的溶胶凝胶制备方法。同时,针对偏磷酸钒氧电导率低的缺点,采用惰性气氛下退火,对产物进行碳包覆,提高了其电导率和电化学性能。
针对传统的合成方法反应时间长、工艺复杂、成本高等缺点,本发明提供了一种工艺简单、原料来源丰富、适合于工业化生产的合成方法,所述方法能够大大缩短反应时间,节约成本,通过该方法合成的碳包覆偏磷酸钒氧[VO(PO3)2]作为锂离子电池负极材料具有较高的充放电容量和较好的循环性能。
本发明的目的是通过如下的技术方案实现的:
一种锂离子电池负极材料偏磷酸钒氧的制备方法,包括如下步骤:
(1)混合前驱体:将磷源和钒源溶于蒸馏水中,保持温度在60-80℃范围内加热搅拌得到胶体,进一步烘干得到干胶体;
(2)预处理:将步骤(1)所述的干胶体研磨,在空气气氛下300-450℃热处理5-6h,随炉冷却后研磨得到粉末状中间产物;
(3)烧结反应:将步骤(2)所述的粉末状中间产物在空气中550-750℃烧结处理10-24h,自然冷却后得到偏磷酸钒氧负极材料。
优选的,步骤(1)中所述的磷源包括磷酸二氢铵(NH4H2PO4)、磷酸氢二铵((NH4)2HPO4)、磷酸铵((NH4)3PO4)、五氧化二磷(P2O5)。
优选的,步骤(1)中所述的钒源包括偏钒酸氨(NH4VO3)、三氧化二钒(V2O3)、二氧化钒(VO2)或五氧化二钒(V2O5)。
优选的,步骤(1)中所述的胶体中钒、磷的摩尔比为1:2。
优选的,步骤(1)所述搅拌的时间为5-8h。
优选的,所述烘干的温度为50-100℃。
优选的,步骤(3)所述烧结反应后的偏磷酸钒氧加入含碳材料,混合后并在300-600℃下再次烧结,合成碳包覆的偏磷酸钒氧,所述烧结反应在所述惰性气体下进行。
优选的,所述的惰性气体包括氩气(Ar)、氮气(N2)、二氧化碳(CO2)或氦气(He)。
优选的,所述烧结的时间为1-10h。
优选的,所述含碳材料是导电碳;进一步优选的,所述含碳材料包括导电聚合物、碳水化合物、乙炔黑、石墨。
优选的,所述含碳材料的重量为偏磷酸钒氧重量的5-20%。
上述的制备方法制备的锂离子电池负极材料偏磷酸钒氧。
上述的锂离子电池负极材料偏磷酸钒氧作为负极材料在锂离子电池中的应用。
相对于现有技术,本发明具有以下几个显著特点:
(1)本发明采用溶胶凝胶的方法合成纯相的偏磷酸钒氧,使反应物在液相环境中达到分子水平的均匀混合,减少了杂质相的产生;预处理和烧结反应均在空气中进行,无需保护气氛,并使钒的价态(+4价)保持不变,适合于工业化生产。
(2)采用溶胶凝胶法使反应时间缩短,反应温度降低;产物结晶性好、结构稳定、原料来源广泛;用产物制得的锂离子电池的可逆容量高,首次和第二次放电容量分别可达:868.5mAh g-1、468.0mAh g-1;同时,使生产成本降低,使反应过程更加容易控制。
(3)针对偏磷酸钒氧电导率低难以作为商业化锂离子电池负极的缺点,采用惰性气氛下进行碳包覆的方法制备了碳包覆的偏磷酸钒氧,不仅工艺简单,而且对其电化学性能有较大提升。
附图说明
图1是实施例1中偏磷酸钒氧粉末的X射线衍射图谱;
图2是实施例1的偏磷酸钒氧粉末的扫描电镜图;
图3是实施例1作为锂离子电池负极材料,电压在0.01-3.0V的前三次循环充放电曲线;
图4是实施例1作为锂离子电池负极材料,电压在0.01-3.0V电压范围内,电流密度100mA/g下的循环性能曲线;
图5是实施例2中偏磷酸钒氧的X射线衍射图谱;
图6是实施例3中碳包覆偏磷酸钒氧粉末的X射线衍射图谱;
图7是实施例3中碳包覆偏磷酸钒氧粉末的扫描电镜图;
图8是实施例3中碳包覆偏磷酸钒氧作为锂离子电池负极材料,电流密度为100mA/g时,电压在0.01-3.0V的前三次循环充放电曲线;
图9是实施例4中碳包覆偏磷酸钒氧的X射线衍射图谱;
图10是实施例4中的碳包覆偏磷酸钒氧作为锂离子电池负极材料,电流密度为100mA/g时,电压在0.01-3.0V的前三次充放电曲线。
具体实施方式
为了更好地理解本发明,下面结合实施例和附图对本发明作进一步说明,但本发明的保护范围并不局限于实施例表示的范围。
实施例1
将NH4VO3和NH4H2PO4按照V:P=1:2的化学计量比称取后,先将NH4H2PO4加入蒸馏水中80℃下持续搅拌直至溶解,再加入NH4VO3,80℃下搅拌得到胶状体。所得胶体置于70℃的鼓风干燥箱中干燥,得到的胶体烘干后研磨,得到前驱体粉末。
制备的前驱体粉末在空气中300℃下预处理5h,随炉自然冷却后研磨得到中间产物,将中间产物粉末在空气中600℃下再次烧结10h,所得粉末的XRD图如图1所示。由图1可知,本发明利用溶胶凝胶的方法得到了纯相的偏磷酸钒氧负极材料,其为四方晶系,空间群为I-42d,XRD谱图中不存在杂质峰,产物纯度高。所述偏磷酸钒氧产物的扫描电镜图如图2所示,其为大小不一的颗粒且表面具有大小不一的孔洞。
将偏磷酸钒氧、PVDF(聚偏氟乙烯)、乙炔黑按照质量比7:2:1的比例混合(总质量为0.2100g),用胶头滴管加入NMP(N-甲基吡咯烷酮)稀释剂(22滴左右),混合均匀后,将其均匀地涂在铜箔上,在烘干后裁成0.8cm*0.8cm的极片,将锂片作为参比电极,与制备的偏磷酸钒氧极片一起组装成半电池。所用电解液和隔膜分别是1mol/L的LiPF6的EC/DMC(体积比为1:1)溶液和聚烯烃(Polyolefin)类隔膜。
偏磷酸钒氧作为锂离子电池负极材料,在电流密度为100mA/g下充放电曲线如图3所示,首次充放电比容量为468.0mAh/g和868.5mAh/g;循环性能如图4所示,30次循环后,放电容量仍为337.4mAh/g,表现出较好的可逆循环性能。
实施例2
将V2O5和(NH4)HPO4按照V:P=1:2的化学计量比称取后,将V2O5和(NH4)HPO4加入80℃的蒸馏水中搅拌3小时后得胶状体;将得到的胶状体放入70℃的鼓风干燥箱中干燥。所得干胶体研磨后在空气中400℃下进行预处理5.5h,自然冷却后,得到粉末状产物;将该粉末状产物再次研磨后在空气中650℃下进行烧结24h,自然冷却后得到偏磷酸钒氧负极材料,产物XRD图谱如图5所示。由图可知,图谱中无杂质峰,产物纯度高,通过此方法可合成纯相的偏磷酸钒氧。
按实施例1的方法组装半电池。
当其作为锂离子电池负极材料时,在100mA/g的电流密度下首次放电比容量为846.5mAh/g,30次循环后放电比容量为348.1mAh/g。
实施例3
将NH4VO3和(NH4)HPO4按照V:P=1:2的化学计量比称取后,先将NH4H2PO4加入蒸馏水中80℃下持续搅拌直至溶解,再加入NH4VO3,80℃下搅拌得到胶状体。所得胶体置于70℃的鼓风干燥箱中干燥,得到的胶体烘干后研磨,得到前驱体粉末。制备的前驱体粉末在空气中300℃下预处理5h,随炉自然冷却后研磨得到中间产物,将中间产物粉末在空气中600℃下再次烧结24h,得到偏磷酸钒氧负极材料。将上述粉末中加入10wt%的科琴黑作为碳源,在行星式球磨机中球磨8h后,在氩气气氛下500℃退火2h,得到碳包覆的偏磷酸钒氧负极材料。
上述碳包覆样品的XRD图如图6所示,所得XRD谱图无任何杂质峰,合成样品为纯相的碳包覆偏磷酸钒氧。其扫描电镜图如图7所示,可看出偏磷酸钒氧样品表面包覆着一些小的碳颗粒,但并不均匀。
按实施例1的方法组装半电池。
该碳包覆的偏磷酸钒氧作为锂离子电池负极材料在100mA/g的电流密度下前三圈的充放电曲线如图8所示,相对于碳包覆之前的充放电比容量皆有提升,30次循环后可保持在425.6mAh/g,相对于碳包覆前样品循环稳定性也有所提高。
实施例4
将V2O5和NH4H2PO4按照V:P=1:2的化学计量比称取后,先将NH4H2PO4加入蒸馏水中80℃下持续搅拌直至溶解,再加入V2O5,80℃下搅拌得到胶状体。所得胶体置于70℃的鼓风干燥箱中干燥,得到的胶体烘干后研磨,得到前驱体粉末。制备的前驱体粉末在空气中300℃下预处理5h,随炉自然冷却后研磨得到中间产物,将中间产物粉末在空气中650℃下再次烧结24h,得到偏磷酸钒氧负极材料。将上述粉末中加入15wt%的蔗糖作为碳源,在行星式球磨机中球磨8h后,在氮气气氛下600℃退火8h,得到碳包覆的偏磷酸钒氧负极材料。
上述碳包覆样品的XRD图如图9所示,由图可知所得样品无杂质,为纯相的碳包覆偏磷酸钒氧。
按实施例1的方法组装半电池。
该碳包覆的偏磷酸钒氧材料作为锂离子电池负极在100mA/g的电流密度下前三圈的充放电曲线如图10所示。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种锂离子电池负极材料偏磷酸钒氧的制备方法,其特征在于,包括如下步骤:
(1)混合前驱体:将磷源和钒源溶于蒸馏水中,保持温度在60-80℃范围内加热搅拌得到胶体,进一步烘干得到干胶体;
(2)预处理:将步骤(1)所述的干胶体研磨,在空气气氛下300-450℃热处理5-6h,随炉冷却后研磨得到粉末状中间产物;
(3)烧结反应:将步骤(2)所述的粉末状中间产物在空气中550-750℃烧结处理10-24h,自然冷却后得到偏磷酸钒氧负极材料。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中所述的磷源包括磷酸二氢铵、磷酸氢二铵、磷酸铵、五氧化二磷。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)中所述的钒源包括偏钒酸氨、三氧化二钒、二氧化钒或五氧化二钒。
4.根据权利要求1所述的制备方法,其特征在于,步骤(1)中所述的胶体中钒、磷的摩尔比为1:2。
5.根据权利要求1所述的制备方法,其特征在于,步骤(1)所述搅拌的时间为5-8h;所述烘干的温度为50-100℃。
6.根据权利要求1所述的制备方法,其特征在于,步骤(3)所述烧结反应后的偏磷酸钒氧加入含碳材料并在300-600℃下再次烧结,合成碳包覆的偏磷酸钒氧,所述烧结反应在所述惰性气体下进行。
7.根据权利要求6所述的制备方法,其特征在于,所述的惰性气体包括氩气、氮气、二氧化碳或氦气;所述烧结的时间为1-10h。
8.根据权利要求6所述的制备方法,其特征在于,所述含碳材料是导电碳,包括导电聚合物、碳水化合物、乙炔黑、石墨;所述含碳材料的重量为偏磷酸钒氧重量的5-20%。
9.权利要求1-8任一项所述的制备方法制备的锂离子电池负极材料偏磷酸钒氧。
10.权利要求9所述的锂离子电池负极材料偏磷酸钒氧作为负极材料在锂离子电池中的应用。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114823166A (zh) * | 2021-12-03 | 2022-07-29 | 曲阜师范大学 | 宽电压窗口的vo(po3)2、制备方法、超级电容器 |
CN114823166B (zh) * | 2021-12-03 | 2024-03-29 | 曲阜师范大学 | 宽电压窗口的vo(po3)2、制备方法、超级电容器 |
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