CN114497478A - 一种多孔纳米α-Fe2O3/Ag负极材料的制备方法 - Google Patents
一种多孔纳米α-Fe2O3/Ag负极材料的制备方法 Download PDFInfo
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 12
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims abstract description 38
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 14
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 239000006258 conductive agent Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 150000002505 iron Chemical class 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000011883 electrode binding agent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 7
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000000539 dimer Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本申请公开了锂电池的制备技术领域中的一种多孔纳米α‑Fe2O3/Ag负极材料的制备方法,原料包括铁盐、表面活性剂、醋酸盐、溶剂、造孔剂和硝酸银,首先通过水热法将铁盐、表面活性剂、醋酸盐、溶剂和造孔剂混合制备成多孔纳米α‑Fe2O3,再通过水热法使硝酸银形成的Ag纳米粒子沉积在α‑Fe2O3的孔道中,得到多孔纳米α‑Fe2O3/Ag负极材料。跟现有技术相比,大大节省了制备时间,并且通过此方法能得到纳米多孔的形貌,醋酸盐可以调节氧化铁颗粒大小,减小了氧化铁的尺寸,再加入造孔剂后,在焙烧过程中形成孔,使得Ag纳米粒子可以沉积到氧化铁的孔道中,材料的导电性更强,进而增强了锂电池的电性能。
Description
技术领域
本发明涉及锂电池的制备技术领域,具体涉及一种多孔纳米α-Fe2O3/Ag负极材料的制备方法。
背景技术
锂离子电池具有能量密度高,循环寿命长、自放电率低、高电压工作、使用温度范围宽、没有“记忆效应”等优点,被认为是电动汽车、混合动力汽车以及新兴智能网络的新电源。目前商用的锂离子电池负极材料石墨的理论容量只有372mAh g-1,无法满足新一代锂离子电池的需要。相比石墨材料,α-Fe2O3的理论容量为1007mAh g-1,且具有高电导率和低成本的优点,因此,α-Fe2O3被认为是最有前途的碳负极材料的替代物之一,然而,α-Fe2O3在脱嵌锂过程中巨大的体积变化会导致电极材料的粉化和比容量的快速衰减。目前,研究工作主要集中于制备纳米结构的α-Fe2O3负极材料来缓解脱嵌锂过程中的体积变化,从而改善其循环稳定性,然而,单一组分的α-Fe2O3纳米结构在循环过程中会发生团聚而导致结构的破坏。因此,制备基于α-Fe2O3纳米结构的复合结构被认为是进一步改善其电化学性能的有效途径之一。
发明内容
本发明针对现有技术的不足,设计一种多孔纳米α-Fe2O3/Ag负极材料的制备方法,进一步改善其电化学性能。
本发明的目的之一是提供一种多孔纳米α-Fe2O3/Ag负极材料的制备方法,原料包括铁盐、表面活性剂、醋酸盐、溶剂、造孔剂和硝酸银,首先通过水热法将铁盐、表面活性剂、醋酸盐、溶剂和造孔剂混合制备成多孔纳米α-Fe2O3,再通过水热法使硝酸银形成的Ag纳米粒子沉积在α-Fe2O3的孔道中,得到多孔纳米α-Fe2O3/Ag负极材料。
进一步细化的,具体包括两个步骤,步骤一、取铁盐、表面活性剂、醋酸盐加入到溶剂和造孔剂混合的溶液中,搅拌至完全溶解后继续搅拌40-60min后,将溶液转移到聚四氟乙烯的内衬中,于150℃~200℃水热15~24h,待温度降到室温时用去离子水和乙醇交替离心4~6次,所得样品为纳米多孔α-Fe2O3;
步骤二、取步骤一的纳米多孔α-Fe2O3加入到硝酸银溶液中搅拌40min~60min,然后将搅拌好的溶液转移到聚四氟乙烯的内衬中,180℃~200℃水热20~30h,待冷却到室温后进行抽滤,经过多次水洗和醇洗后,将产物放进30℃~50℃的真空干燥箱干燥,得到多孔纳米α-Fe2O3/Ag负极材料。
进一步,原料按照质量份数计为:2~7份铁盐、1~5份表面活性剂、5~10份醋酸盐、16~50 份溶剂、19~66份造孔剂和0.05~0.1份的硝酸银。
优选的,原料按照质量份数计为:2~4份铁盐、1~3份表面活性剂、5~8份醋酸盐、16~40 份溶剂、19~30份造孔剂和0.05~0.1份的硝酸银。
进一步,原料按照质量份数计为:2份铁盐、2份表面活性剂、6份醋酸盐、40份溶剂、20份造孔剂和0.05~0.1份的硝酸银。
进一步,所述溶剂为无水乙醇,所述造孔剂为甲酰胺或N-N二甲基甲酰胺,所述铁盐为氯化铁、硝酸铁或醋酸铁,所述醋酸盐为醋酸钠或者醋酸钾。
进一步,所述表面活性剂是聚乙烯吡咯烷酮或N-乙烯吡咯烷酮。
本发明的目的之二是提供通过一种负极极片,使用上述方法制备的α-Fe2O3/Ag负极材料进行制备。
进一步,在制备时,包括将α-Fe2O3/Ag负极材料、负极分散剂、负极粘结剂和负极导电剂均匀分散在去离子水中得负极浆料,将负极浆料涂覆在铜箔上后经干燥、辊压、分切后得负极极片。
进一步,各组分的质量百分比为:95.5%的α-Fe2O3/Ag负极材料,2%的负极分散剂, 1.5%的负极粘结剂,1%的负极导电剂,其中,负极分散剂为羧甲基纤维素钠,负极粘结剂为丁苯胶乳,负极导电剂为乙炔黑。
本发明的目的之三是提供一种锂离子电池,还包括正极片的制备,将正极活性材料、正极分散剂、正极粘结剂和正极导电剂均匀分散在NMP中得正极浆料,将正极浆料涂覆在铝箔上后经干燥、辊压、分切后得正极极片;将正极极片和负极极片组装到锂离子电池中。
其中,正极极片各组分的质量百分比为正极活性材料94~97%,正极粘结剂1~3.5%,正极导电剂1~5%,其中,正极活性材料为NCM三元材料,正极粘结剂为聚偏氟乙烯,正极导电剂为炭黑。
本发明采用两步水热法制备多孔纳米α-Fe2O3/Ag负极材料,与传统的氧化铁的制备方法相较,大大节省了制备时间,并且通过此方法能得到纳米多孔的形貌,醋酸盐可以调节氧化铁颗粒大小,减小了氧化铁的尺寸,再加入造孔剂后,在焙烧过程中形成孔,使得Ag纳米粒子可以沉积到氧化铁的孔道中,材料的导电性更强,进而增强了电性能。
本发明的工作原理:由于多孔纳米α-Fe2O3/Ag复合材料中的纳米α-Fe2O3具有多孔结构,展现出良好的传质和吸附能力。将银纳米粒子沉积到孔道内,能有效地避免纳米银的团聚,提升纳米银的使用效率;并且欲使用时域有限差分法(FDTD)对银纳米粒子局部电磁场强度进行模拟计算,选取波长为532nm的激光激发单一银纳米粒子及银纳米粒子二聚体。银纳米粒子二聚体结点处的电场强度将高于单一银纳米粒子。银纳米粒子二聚体电场强度的显著增加是由于两个耦合的银纳米颗粒组成的间隙位点(热点)处与局域表面等离子共振 (LSPR)相关联的高度集中的电磁场引起的,增强了复合材料的导电性。所以多孔纳米α-Fe2O3/Ag复合材料的倍率性能要优于纯的α-Fe2O3。
具体实施方式
下面通过具体实施方式进一步详细说明:
实施例1,多孔纳米α-Fe2O3/Ag负极材料和利用其制备扣式电池的具体步骤如下:
1、制备α-Fe2O3:取铁盐2份,表面活性剂2份,醋酸盐6份加入到由40份溶剂和20 份造孔剂混合的溶液中,搅拌至完全溶解后继续搅拌40~60min后,将溶液转移到聚四氟乙烯的内衬中,150℃~200℃水热18h,待温度降到室温时用去离子水和乙醇交替离心4~6次,所得样品即为纳米多孔α-Fe2O3;
2、制备α-Fe2O3/Ag负极材料:按照步骤1)的方法制备4组α-Fe2O3、将四组α-Fe2O3分别加入到含0.05、0.065、0.08和0.1份硝酸银溶液中搅拌40min~60min,然后将搅拌好的溶液转移到聚四氟乙烯的内衬中,180℃~200℃水热24h,待冷却到室温后进行抽滤,经过多次水洗和醇洗后,将所得到的产物放进30℃~50℃的真空干燥箱干燥10h,即得到不同硝酸银比例的α-Fe2O3/Ag负极材料;
3、制备正极片:将正极活性材料、正极分散剂、正极粘结剂和正极导电剂均匀分散在 NMP中得正极浆料,将正极浆料涂覆在铝箔上后经干燥、辊压、分切后得正极极片。正极材料中各组分的质量百分比为:正极材料94~97%,正极粘结剂1~3.5%,正极导电剂1~5%。其中,正极活性材料为NCM三元材料,正极粘结剂为聚偏氟乙烯(PVDF),正极导电剂为炭黑。涂布完成后放入烘箱干燥,温度120~150℃,干燥后得到正极片;
4、制备α-Fe2O3/Ag的负极片:将α-Fe2O3/Ag负极材料、负极分散剂、负极粘结剂和负极导电剂均匀分散在去离子水中得负极浆料,将负极浆料涂覆在铜箔上后经干燥、辊压、分切后得负极极片。α-Fe2O3/Ag负极材料中各组分的质量百分比为:α-Fe2O3/Ag负极材料95.5%,负极分散剂2%,负极粘结剂1.5%,负极导电剂1%。其中,负极分散剂为羧甲基纤维素钠,负极粘结剂为丁苯胶乳,负极导电剂为乙炔黑。涂布完成后放入烘箱干燥,温度120~150℃,干燥后得到负极片;
5、将上述制备好的正负极片采用打孔器截取直径为16mm的圆形电极片,2300膜(美国产)为隔膜,使用电解液LiPF6/EC+DMC+EMC,在氩气保护的手套箱中组装CR2032型对称型扣式锂离子电池。
本实施例的1份相当于1g。
根据测试结果证明,多孔纳米α-Fe2O3/Ag复合材料的倍率性能要优于纯的α-Fe2O3。且当硝酸银溶液为0.065份时,多孔纳米α-Fe2O3/Ag复合材料的倍率性能最高。
以上所述的仅是本发明的实施例,方案中公知的具体结构及特性等常识在此未作过多描述。应当指出,对于本领域的技术人员来说,在不脱离本发明结构的前提下,还可以作出若干变形和改进,这些也应该视为本发明的保护范围,这些都不会影响本发明实施的效果和专利的实用性。本申请要求的保护范围应当以其权利要求的内容为准,说明书中的具体实施方式等记载可以用于解释权利要求的内容。
Claims (10)
1.一种多孔纳米α-Fe2O3/Ag负极材料的制备方法,其特征在于,原料包括铁盐、表面活性剂、醋酸盐、溶剂、造孔剂和硝酸银,首先通过水热法将铁盐、表面活性剂、醋酸盐、溶剂和造孔剂混合制备成多孔纳米α-Fe2O3,再通过水热法使硝酸银形成的Ag纳米粒子沉积在α-Fe2O3的孔道中,得到多孔纳米α-Fe2O3/Ag负极材料。
2.根据权利要求1所述的一种多孔纳米α-Fe2O3/Ag负极材料的制备方法,其特征在于:具体包括两个步骤,步骤一、取铁盐、表面活性剂、醋酸盐加入到溶剂和造孔剂混合的溶液中,搅拌至完全溶解后继续搅拌40-60min后,将溶液转移到聚四氟乙烯的内衬中,于150℃~200℃水热15~24h,待温度降到室温时用去离子水和乙醇交替离心4~6次,所得样品为纳米多孔α-Fe2O3;
步骤二、取步骤一的纳米多孔α-Fe2O3加入到硝酸银溶液中搅拌40min~60min,然后将搅拌好的溶液转移到聚四氟乙烯的内衬中,180℃~200℃水热20~30h,待冷却到室温后进行抽滤,经过多次水洗和醇洗后,将产物放进30℃~50℃的真空干燥箱干燥,得到多孔纳米α-Fe2O3/Ag负极材料。
3.根据权利要求2所述的一种多孔纳米α-Fe2O3/Ag负极材料的制备方法,其特征在于:原料按照质量份数计为:2~7份铁盐、1~5份表面活性剂、5~10份醋酸盐、16~50份溶剂、19~66份造孔剂和0.05~0.1份的硝酸银。
4.根据权利要求3所述的一种多孔纳米α-Fe2O3/Ag负极材料的制备方法,其特征在于:所述溶剂为无水乙醇,所述造孔剂为甲酰胺或N-N二甲基甲酰胺,所述铁盐为氯化铁、硝酸铁或醋酸铁,所述醋酸盐为醋酸钠或者醋酸钾。
5.根据权利要求4所述的一种多孔纳米α-Fe2O3/Ag负极材料的制备方法,其特征在于:所述表面活性剂是聚乙烯吡咯烷酮或N-乙烯吡咯烷酮。
6.一种负极极片,包括使用权利要求1~5任一所述方法制备的α-Fe2O3/Ag负极材料进行制备。
7.根据权利要求6所述的负极极片,其特征在于:在制备时,包括将α-Fe2O3/Ag负极材料、负极分散剂、负极粘结剂和负极导电剂均匀分散在去离子水中得负极浆料,将负极浆料涂覆在铜箔上后经干燥、辊压、分切后得负极极片。
8.根据权利要求7所述的负极极片,其特征在于:各组分的质量百分比为:93~96%的α-Fe2O3/Ag负极材料,1~3%的负极分散剂,1~2%的负极粘结剂,1~2%的负极导电剂,其中,负极分散剂为羧甲基纤维素钠,负极粘结剂为丁苯胶乳,负极导电剂为乙炔黑。
9.应用权利要求8所述的负极极片制备的锂离子电池,其特征在于:还包括正极片的制备,将正极活性材料、正极分散剂、正极粘结剂和正极导电剂均匀分散在NMP中得正极浆料,将正极浆料涂覆在铝箔上后经干燥、辊压、分切后得正极极片;将正极极片和负极极片组装到锂离子电池中。
10.根据权利要求9所述的锂离子电池,其特征在于:正极极片各组分的质量百分比为正极活性材料94~97%,正极粘结剂1~3.5%,正极导电剂1~5%,其中,正极活性材料为NCM三元材料,正极粘结剂为聚偏氟乙烯,正极导电剂为炭黑。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114920217A (zh) * | 2022-06-14 | 2022-08-19 | 浙江工业大学 | 一种高吸波性能多孔铁基氮化物材料及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110236747A1 (en) * | 2010-03-29 | 2011-09-29 | Kan-Sen Chou | Composite material for negative electrode, method for fabricating the same and electrochemical device using the same |
KR20150011552A (ko) * | 2013-07-23 | 2015-02-02 | 한국세라믹기술원 | 리튬이차전지용 산화제2철계 음극활물질의 제조방법 및 이를 이용한 리튬이차전지의 제조방법 |
CN105688909A (zh) * | 2014-11-27 | 2016-06-22 | 中国科学院大连化学物理研究所 | 一种银/金属氧化物多孔材料、其制备方法和应用 |
KR20170126196A (ko) * | 2016-05-09 | 2017-11-17 | 한국과학기술원 | 금속 나노입자가 코팅된 금속-금속산화물 또는 금속산화물-금속산화물의 이종 복합체로 구성된 일차원 다공성 나노튜브, 이를 포함하는 고용량 이차전지용 음극활물질 및 그 제조방법 |
KR20210113893A (ko) * | 2020-03-09 | 2021-09-17 | 홍익대학교 산학협력단 | 표면 플라즈마 공명 현상을 이용한 리튬 이차 전지 및 그 제조 방법 |
-
2021
- 2021-12-30 CN CN202111654703.2A patent/CN114497478A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110236747A1 (en) * | 2010-03-29 | 2011-09-29 | Kan-Sen Chou | Composite material for negative electrode, method for fabricating the same and electrochemical device using the same |
KR20150011552A (ko) * | 2013-07-23 | 2015-02-02 | 한국세라믹기술원 | 리튬이차전지용 산화제2철계 음극활물질의 제조방법 및 이를 이용한 리튬이차전지의 제조방법 |
CN105688909A (zh) * | 2014-11-27 | 2016-06-22 | 中国科学院大连化学物理研究所 | 一种银/金属氧化物多孔材料、其制备方法和应用 |
KR20170126196A (ko) * | 2016-05-09 | 2017-11-17 | 한국과학기술원 | 금속 나노입자가 코팅된 금속-금속산화물 또는 금속산화물-금속산화물의 이종 복합체로 구성된 일차원 다공성 나노튜브, 이를 포함하는 고용량 이차전지용 음극활물질 및 그 제조방법 |
KR20210113893A (ko) * | 2020-03-09 | 2021-09-17 | 홍익대학교 산학협력단 | 표면 플라즈마 공명 현상을 이용한 리튬 이차 전지 및 그 제조 방법 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114920217A (zh) * | 2022-06-14 | 2022-08-19 | 浙江工业大学 | 一种高吸波性能多孔铁基氮化物材料及其制备方法 |
CN114920217B (zh) * | 2022-06-14 | 2023-10-31 | 浙江工业大学 | 一种高吸波性能多孔铁基氮化物材料及其制备方法 |
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