CN113651348A - 一种三氧化二铝包覆氟化碳及其制备方法、应用和锂电池 - Google Patents
一种三氧化二铝包覆氟化碳及其制备方法、应用和锂电池 Download PDFInfo
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- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 title claims abstract description 47
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 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 abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000010992 reflux Methods 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 239000007774 positive electrode material Substances 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000007772 electrode material Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000463 material Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- WDEOTCWPXLWTRP-UHFFFAOYSA-N [C+4].[O-2].[Al+3] Chemical compound [C+4].[O-2].[Al+3] WDEOTCWPXLWTRP-UHFFFAOYSA-N 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
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- 238000001291 vacuum drying Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
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Abstract
本发明涉及锂电池技术领域,具体涉及一种三氧化二铝包覆氟化碳及其制备方法、应用和锂电池。制备方法包括1)向氟化碳中加入乙醇后,与硝酸铝水溶液混合,搅拌均匀;2)向步骤1)所得混合物中加入尿素和氨水;3)将步骤2)所得混合溶液回流加热,逐渐产生氢氧化铝沉淀;4)将步骤3)所得混合物洗涤、过滤并干燥;5)将步骤4)干燥后所得混合物取出,经煅烧后,冷却至室温,得到目标产物;该三氧化二铝包覆氟化碳可作为电极材料应用;锂电池为以该三氧化二铝包覆氟化碳作为正极材料组装的锂电池。所得三氧化二铝包覆氟化碳具有较好的倍率性能,可作为电极材料使用。
Description
技术领域
本发明涉及锂电池技术领域,具体涉及一种三氧化二铝包覆氟化碳及其制备方法、应用和锂电池。
背景技术
氟化碳材料是碳材料的重要衍生物,其具有极低的表面能和层间能,化学稳定性和热稳定性优异,理论比容量高,因此,其在固体润滑、防腐防污和电池电极材料等领域有着重要的应用。
锂/氟化碳电池是现有比能量最高的一次电池,理论比能量为2180Wh/kg,锂/氟化碳电池还具有电压稳定、工作温度宽、自放电小、寿命长等特点,被认为是最具有潜力的电池之一。锂/氟化碳电池工作温度范围为-60℃~180℃,可满足航空航天等极端环境要求。
然而,由于C-F键的强共价特性,氟化碳的导电性差,并且氟化碳的表面能低,与电解液渗透性差,因此氟化碳作电极时,容易引起极化,导致锂/氟化碳电池倍率性能较差,放电平台较低,远不及其理论放电平台,不能满足高倍率放电要求。
发明内容
针对普通锂/氟化碳电池不能满足高倍率放电要求的技术问题,本发明提供一种三氧化二铝包覆氟化碳及其制备方法、应用和锂电池,使用回流加热的方法反应生成氢氧化铝胶体,在这个反应过程中,氟化碳表面部分分解,生成碳,与氢氧化铝胶体混合形成混合包覆层,并通过煅烧加热的方式,将氢氧化铝转化为三氧化二铝,形成三氧化二铝-碳包覆层,所得三氧化二铝包覆氟化碳具有较好的倍率性能,可作为电极材料使用。
第一方面,本发明提供一种三氧化二铝包覆氟化碳的制备方法,包括如下步骤:
1)向氟化碳中加入乙醇后,与硝酸铝水溶液混合,搅拌均匀;
2)向步骤1)所得混合物中加入尿素和氨水;
3)将步骤2)所得混合溶液回流加热,逐渐产生氢氧化铝沉淀;
4)将步骤3)所得混合物洗涤、过滤并干燥;
5)将步骤4)干燥后所得混合物取出,经煅烧后,冷却至室温,得到目标产物。
进一步的,氟化碳与硝酸铝的摩尔比为1:0~1,氟化碳与尿素的摩尔比为1:0~1,氟化碳与氨水的摩尔体积比(mol/L)为1:0~1,氨水浓度为1%~28%。
进一步的,硝酸铝水溶液中硝酸铝的质量分数为0%~60%。
进一步的,回流加热温度为80~110℃,回流加热时间为0~10h。
进一步的,洗涤、过滤方法可采取离心、抽滤和/或其他现有洗涤、过滤方法中的至少一种;
干燥可采取水浴加热蒸发、干燥箱烘干、真空干燥、自然风干和/或其他现有干燥方法中的至少一种,干燥温度为20~100℃;
煅烧后冷却可采取程序控制缓慢降温、自然冷却、将样品投入水中淬火和/或其他现有冷却方法中的至少一种。
进一步的,煅烧温度为100~600℃,煅烧时间为0~24h,煅烧环境为惰性气体环境或真空环境。
第二方面,本发明提供一种采用上述方法制得的三氧化二铝包覆氟化碳。
第三方面,本发明提供一种上述三氧化二铝包覆氟化碳作为电极材料的应用,优选为锂离子电池正极材料,进一步优选为高倍率锂电池正极材料。
第四方面,本发明提供一种锂电池,锂电池以上述三氧化二铝包覆氟化碳作为正极材料,并在充满氩气的手套箱中进行组装。
本发明的有益效果在于,
本发明通过回流加热的方法反应生成氢氧化铝胶体,在这个反应过程中,氟化碳表面部分分解,生成碳,与氢氧化铝胶体混合形成混合包覆层,均匀包覆在氟化碳表面,并通过煅烧加热的方式,将氢氧化铝转化为三氧化二铝,形成三氧化二铝-碳包覆层,在电化学反应过程中,该包覆层可以增加材料的导电性,中和电化学反应过程中生成的HF,保护正极材料和电池,三氧化二铝包覆氟化碳材料粉体粒径在微米级,表现出优异的电化学性能。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,对于本领域普通技术人员而言,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是实施例1材料的扫描电子显微镜图片;
图2是实施例4锂电池在5C倍率下的放电性能图;
图3是实施例5锂电池在5C倍率下的放电性能图;
图4是对比例1锂电池在5C倍率下的放电性能图。
具体实施方式
为了使本技术领域的人员更好地理解本发明中的技术方案,下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都应当属于本发明保护的范围。
下述实施例所使用的氟化碳的氟碳比约在1,相对分子质量约为31。
实施例1
取10g氟化碳,加入5mL乙醇,搅拌至泥浆状。取2.13g硝酸铝,加水溶解,配置5%的硝酸铝溶液,将配置好的硝酸铝水溶液加入至盛有泥浆状氟化碳的容器中,形成混合溶液,搅拌均匀。将所得混合溶液中加入0.9g尿素和10mL浓度为25%的氨水,将混合溶液转移至圆底烧瓶中,搅拌,80℃下回流加热1h,逐渐产生氢氧化铝沉淀。将混合溶液过滤,并使用去离子水洗涤3次,将滤渣转移至烘箱中,80℃干燥24h,将干燥后的滤渣转移至管式炉中,通氮气,400℃煅烧6h,所得目标产物即为的三氧化二铝包覆氟化碳材料。如图1所示,三氧化二铝包覆氟化碳材料粒径在微米级。
实施例2
取100g氟化碳,加入30mL乙醇,搅拌至泥浆状。取42.6g硝酸铝,加水溶解,配置10%的硝酸铝溶液,将配置好的硝酸铝水溶液加入至盛有泥浆状氟化碳的容器中,形成混合溶液,搅拌均匀。将所得混合溶液中加入20g尿素和200mL浓度为25%的氨水,将混合溶液转移至圆底烧瓶中,搅拌,105℃下回流加热4h,逐渐产生氢氧化铝沉淀。将混合溶液抽滤,并使用去离子水洗涤3次,将滤渣转移至烘箱中,100℃干燥24h,将干燥后的滤渣转移至管式炉中,通氮气,160℃煅烧24h,所得目标产物即为三氧化二铝包覆氟化碳材料。
实施例3
取50g氟化碳,加入200mL乙醇,搅拌至泥浆状。取213g硝酸铝,加水溶解,配置8%的硝酸铝溶液,将配置好的硝酸铝水溶液加入至盛有泥浆状氟化碳的容器中,形成混合溶液,搅拌均匀。将所得混合溶液中加入60g尿素和1000mL浓度为5%的氨水,将混合溶液转移至圆底烧瓶中,搅拌,100℃下回流加热6h,逐渐产生氢氧化铝沉淀。将混合溶液离心过滤,并使用去离子水洗涤3次,将滤渣转移至烘箱中,90℃干燥24h,将干燥后的滤渣转移至加热炉中,600℃煅烧1h,所得目标产物即为三氧化二铝包覆氟化碳材料。
实施例4
以实施例1制得的三氧化二铝包覆氟化碳材料作为正极材料,将所得三氧化二铝包覆氟化碳正极材料、导电炭黑和PVDF按80:10:10的比例混合于N-甲基吡咯烷酮中,研磨成膏状,涂布到铝箔上;在120℃真空干燥12h,裁成直径12mm的电极片;将称重后的电极片做成正极,以金属锂为负极,以聚乙烯微孔膜为隔膜,以1M LiClO4(DME+PC)为电解液,在充满氩气的手套箱中组装成锂电池。
实施例5
以实施例2制得的三氧化二铝包覆氟化碳材料作为正极材料,其余选择同实施例4,在充满氩气的手套箱中组装成锂电池。
对比例1
以实施例1的原料氟化碳作为正极材料,其余选择同实施例4,在充满氩气的手套箱中组装成锂电池。
对实施例4、5的锂电池进行电化学性能测试,结果如图2、3所示。对于实施例4的锂电池,在5C的倍率下,1.5V以上的放电比容量达到743.9mAh/g,2V以上的放电比容量达到624.9mAh/g,放电平台2.14V;对于实施例5的锂电池,在5C的倍率下,1.5V以上的放电比容量达到575.0mAh/g,2V以上的放电比容量达到489.0mAh/g,放电平台2.22V。实施例4、5的电化学性能检测结果说明本发明方法制备的三氧化二铝包覆氟化碳具有良好的倍率性能。
对对比例1的锂电池进行电化学性能测试,结果如图4所示,在5C的倍率下,1V以上的放电比容量为154.1mAh/g,放电平台为1.1V,说明原料氟化碳倍率性能较差。
综上所述,与原料氟化碳相比,通过本发明方法制备的三氧化二铝包覆氟化碳,电化学性能更优异,尤其是在高倍率下,放电平台更高。
尽管通过参考附图并结合优选实施例的方式对本发明进行了详细描述,但本发明并不限于此。在不脱离本发明的精神和实质的前提下,本领域普通技术人员可以对本发明的实施例进行各种等效的修改或替换,而这些修改或替换都应在本发明的涵盖范围内/任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到变化或替换,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种三氧化二铝包覆氟化碳的制备方法,其特征在于,包括如下步骤:
1)向氟化碳中加入乙醇后,与硝酸铝水溶液混合,搅拌均匀;
2)向步骤1)所得混合物中加入尿素和氨水;
3)将步骤2)所得混合溶液回流加热,逐渐产生氢氧化铝沉淀;
4)将步骤3)所得混合物洗涤、过滤并干燥;
5)将步骤4)干燥后所得混合物取出,经煅烧后,冷却至室温,得到目标产物。
2.如权利要求1所述的制备方法,其特征在于,氟化碳与硝酸铝的摩尔比为1:0~1,氟化碳与尿素的摩尔比为1:0~1,氟化碳与氨水的摩尔体积比为1:0~1,氨水浓度为1%~28%。
3.如权利要求1所述的制备方法,其特征在于,硝酸铝水溶液中硝酸铝的质量分数为0%~60%。
4.如权利要求1所述的制备方法,其特征在于,回流加热温度为80~110℃,回流加热时间为0~10h。
5.如权利要求1所述的制备方法,其特征在于,干燥温度为20~100℃。
6.如权利要求1所述的制备方法,其特征在于,煅烧温度为100~600℃,煅烧时间为0~24h,煅烧环境为惰性气体环境或真空环境。
7.一种采用如权利要求1所述的制备方法制得的三氧化二铝包覆氟化碳。
8.一种如权利要求7所述的三氧化二铝包覆氟化碳作为电极材料的应用。
9.如权利要求8所述的应用,其特征在于,所述电极材料为锂电池正极材料。
10.一种锂电池,其特征在于,锂电池以如权利要求7所述的三氧化二铝包覆氟化碳作为正极材料,并在充满氩气的手套箱中进行组装。
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Publication number | Priority date | Publication date | Assignee | Title |
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CN117393786A (zh) * | 2023-12-11 | 2024-01-12 | 中国电子科技集团公司第十八研究所 | 一种高比能海水电池及制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010238664A (ja) * | 2009-03-13 | 2010-10-21 | Panasonic Corp | リチウム一次電池用正極およびこれを用いたリチウム一次電池 |
CN102280614A (zh) * | 2011-07-07 | 2011-12-14 | 天津大学 | 一种锂硫电池的硫正极的制备方法 |
US20120126182A1 (en) * | 2010-11-24 | 2012-05-24 | U.S. Government as reperesented by the Secretary of the Army | Fluorinated carbon composite cathode for a high-energy lithium battery |
CN105655588A (zh) * | 2016-04-08 | 2016-06-08 | 北京工业大学 | 一种二氧化硅改性的氟化碳材料及制备方法 |
CN106206056A (zh) * | 2016-07-29 | 2016-12-07 | 武汉理工大学 | 一种钴铝水滑石/氟化石墨烯复合材料及其制备方法 |
CN106384812A (zh) * | 2016-10-13 | 2017-02-08 | 江苏超电新能源科技发展有限公司 | 一种表面改性氟化碳材料及其方法与应用 |
-
2021
- 2021-08-12 CN CN202110926458.XA patent/CN113651348B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010238664A (ja) * | 2009-03-13 | 2010-10-21 | Panasonic Corp | リチウム一次電池用正極およびこれを用いたリチウム一次電池 |
US20120126182A1 (en) * | 2010-11-24 | 2012-05-24 | U.S. Government as reperesented by the Secretary of the Army | Fluorinated carbon composite cathode for a high-energy lithium battery |
CN102280614A (zh) * | 2011-07-07 | 2011-12-14 | 天津大学 | 一种锂硫电池的硫正极的制备方法 |
CN105655588A (zh) * | 2016-04-08 | 2016-06-08 | 北京工业大学 | 一种二氧化硅改性的氟化碳材料及制备方法 |
CN106206056A (zh) * | 2016-07-29 | 2016-12-07 | 武汉理工大学 | 一种钴铝水滑石/氟化石墨烯复合材料及其制备方法 |
CN106384812A (zh) * | 2016-10-13 | 2017-02-08 | 江苏超电新能源科技发展有限公司 | 一种表面改性氟化碳材料及其方法与应用 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117393786A (zh) * | 2023-12-11 | 2024-01-12 | 中国电子科技集团公司第十八研究所 | 一种高比能海水电池及制备方法 |
CN117393786B (zh) * | 2023-12-11 | 2024-02-23 | 中国电子科技集团公司第十八研究所 | 一种高比能海水电池及制备方法 |
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