CN113023705A - 一种富氢碳材料的制备方法及应用于锂-钠-钾储能 - Google Patents
一种富氢碳材料的制备方法及应用于锂-钠-钾储能 Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 49
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004146 energy storage Methods 0.000 title abstract description 10
- UTBYQPSPFXHANA-UHFFFAOYSA-N [K].[Na].[Li] Chemical compound [K].[Na].[Li] UTBYQPSPFXHANA-UHFFFAOYSA-N 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000003990 capacitor Substances 0.000 claims description 22
- 229910001415 sodium ion Inorganic materials 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical group CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 239000000661 sodium alginate Substances 0.000 claims description 8
- 235000010413 sodium alginate Nutrition 0.000 claims description 8
- 229940005550 sodium alginate Drugs 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 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
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 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 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012075 bio-oil Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000007773 negative electrode material Substances 0.000 abstract description 7
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 9
- 239000011324 bead Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000000017 hydrogel Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012704 polymeric precursor Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 229940072056 alginate Drugs 0.000 description 3
- 235000010443 alginic acid Nutrition 0.000 description 3
- 229920000615 alginic acid Polymers 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002785 Croscarmellose sodium Polymers 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
本发明属于无机纳米材料和储能技术领域,涉及一种富氢碳负极材料的制备方法,包括:碳源溶于去离子水中配制成质量分数为2~10%的溶液,标记为溶液A;催化剂溶解在去离子水配制成质量分数为1~5%的溶液,标记为溶液B;将A溶液滴加到B溶液中,搅拌下充分反应后,洗涤、冻干;干燥产物于惰性气氛中600~1000℃碳化1~5 h,酸洗,即得。本发明以自模板法将聚合物前驱体制备成富氢碳材料,无需掺杂,反应条件简单,使用的溶剂价格便宜,无毒无害,合成的富氢碳材料本身具有较大的无序度和比表面积,提供更多的活性位点,表现出优异的可逆比容量、倍率性能、循环性能和长循环寿命,有利于满足实际需求。
Description
技术领域
本发明属于无机纳米材料和储能技术领域,涉及富氢碳材料,尤其涉及一种富氢碳负极材料的制备方法及应用于锂-钠-钾储能。
背景技术
面对能源枯竭和环境污染带来的压力,人类开始将目光放到新能源的开发与利用上,其中能源的储存是不可或缺的环节,开发出高能量密度和高功率密度的电化学储能系统成为迫切且严峻的问题。二次电池如锂离子电池、钠离子电池等具有能量密度高、环境友好等特点;超级电容器具有功率密度高、充放电时间短、循环寿命长等特点,这两种储能器件均在实际应用中备受关注。
碱金属(锂/钠/钾)离子电容器作为碱金属离子电池和超级电容器的结合体,兼具碱金属(锂/钠/钾)离子电池的高能量密度和超级电容器的高功率密度和超长循环寿命,很好地满足了对新一代储能器件的要求。
电极材料是决定储能器件的电化学性能的关键要素之一。碳材料因为其导电性好,热稳定性高,具有良好的层状结构,适合金属离子的嵌入和脱出,广泛应用于电池和电容器的负极材料,如:石墨烯,碳纳米管,多孔碳等。单纯的碳电极材料的实际比电容和能量密度较低,循环稳定性差,限制了碳材料在储能器件中的进一步应用和发展。近年来,已开发出多种改善碳材料电化学性能的方法,其中,杂原子掺杂被认为是增加电子传导性、表面积及活性位点的有效策略,但掺杂过程复杂且难以实现对结构的精准控制,制备工艺相对复杂。
寻找一种制备方法简单、成本低廉、结构稳定的新型富氢碳材料,具有十分重要的意义。
发明内容
针对碳材料制备方法繁琐及作为电极材料的能量密度低和循环稳定性差的问题,本发明提供一种富氢碳材料的制备方法。
技术方案
一种富氢碳材料的制备方法,包括如下步骤:
A. 碳源溶于去离子水中配制成质量分数为2~10%的溶液, 标记为溶液A,其中所述碳源为海藻酸钠、羧甲基纤维素钠或生物油;
B. 催化剂溶解在去离子水配制成质量分数为1~5%的溶液, 标记为溶液B,其中所述催化剂为氯化铁、氯化锌或氯化钠;
C. 将A溶液滴加到B溶液中,搅拌下充分反应后,洗涤、冻干;
D. 干燥产物于惰性气氛中600~1000℃碳化1~5 h,酸洗,即得。
本发明较优公开例中,步骤C中所述冻干,其温度-100~-20℃,冻干时间12~72h。
本发明较优公开例中,步骤D中所述惰性气体为氩气或氮气。
本发明较优公开例中,步骤D中所述酸洗,所用的溶液为质量分数为30%的盐酸溶液或硫酸溶液。
本发明较优公开例中,步骤D中所述碳化,所用设备为管式炉或箱式炉,升温速率为2~15℃·min−1。
根据本发明所述方法制备得到的富氢碳材料,应用于锂/钠/钾离子电池或电容器领域,但又不限于上述领域。
一种高能量和高功率密度的锂离子超级电容器,包括正极片、负极片、隔膜、垫片、垫圈及电解液,所述正极片为科琴导电炭黑,所述负极片由负极材料经过预锂化而成,所述电解液为1 M LiPF6。
进一步的,所述负极片是在铜片表面涂覆由负极活性材料、导电剂、分散剂及粘结剂按质量比为8:1:1组成的负极浆料。其中,所述负极活性材料为富氢碳材料;所述导电剂为科琴导电炭黑Ketjenblack EC-600JD;所述分散剂为氮甲基吡咯烷酮(NMP);所述粘结剂为油性粘结剂聚偏氟乙烯(PVDF)。
进一步的,所述预锂化是将上述负极材料组装成2032纽扣电池,在0.01~3 V电势窗口下,以100 mA/g电流密度下预锂化十圈,得到负极片。
将上述负极片与正极片以六氟磷酸锂为电解液,组装成全电池器件,在0.01~4.5V电势窗口下,以不同扫描速率测得其循环伏安曲线,在电流密度下测试其倍率性能及循环性能。
本发明所制得的富氢碳材料在锂/钠/钾离子电池及锂/钠/钾离子电容器中都具有良好的应用前景,所述富氢碳材料应用于锂离子电容器(LIC)和钠离子电容器(SIC)时,二者均具有高能量/功率密度(LIC:151.2 Wh kg−1 / 28.4 kW kg−1;SIC:100.5 Wh kg−1 /18.6 kW kg−1),并具有出色的倍率和循环性能。可将其作为碱金属电容器储能器件的负极材料。
所述的富氢碳材料是指含有大量氢的碳材料,为本领域专有名词,属于清楚表述。
有益效果
本发明以自模板法将聚合物前驱体制备成富氢碳材料,无需掺杂,反应条件简单,使用的溶剂价格便宜,无毒无害,符合环境绿色友好的要求,有着极其广泛的应用前景。合成的富氢碳材料本身具有较大的无序度和比表面积,提供了更多的活性位点,表现出优异的可逆比容量、倍率性能和循环性能。本发明制备的富氢碳材料表现出优异的能量/功率密度和长循环寿命,有利于满足实际需求。
附图说明
图1. 实施例1制备的富氢碳材料的扫描电镜图片(SEM);
图2. 实施例1制备的富氢碳材料的透射电镜图片(TEM);
图3. 实施例1制备的富氢碳材料的X射线粉末衍射图(XRD);
图4. 实施例1制备的富氢碳材料的傅立叶变换红外光谱图(FTIR);
图5. 实施例1制备的富氢碳材料的固体核磁共振谱图(MAS-ss-NMR);
图6. 实施例1、2、3制备的富氢碳材料的元素分析图(EA);
图7. 实施例1制备的富氢碳材料用于钠离子电池后的倍率和循环性能曲线;
图8. 实施例1制备的富氢碳材料组装成锂离子电容器和钠离子电容器后的循环稳定性图。
具体实施方式
下面结合实施例对本发明进行详细说明,以使本领域技术人员更好地理解本发明,但本发明并不局限于以下实施例。
实施例1
一种富氢碳材料的制备方法,包括如下步骤:
A、在连续磁力搅拌下,将2 g聚合前体海藻酸钠(SA)溶于100 mL去离子水(DI)中,形成质量分数为2%的水溶液,标记为溶液A;
B、将1 g的无水氯化铁FeCl3溶解在100 mL去离子水形成质量分数为1%的水溶液,标记为溶液B;
C、在磁力搅拌下,将溶液A缓慢加入溶液B中,得到交联的海藻酸铁(IA)微凝胶珠,通过使用冷冻干燥机将洗涤的IA水凝胶珠粒冷冻干燥以蒸发水分;
D、将冷冻干燥的产物在Ar气氛下在水平管式炉中碳化2小时,碳化温度为600 ℃,将产物用1M盐酸(30%)处理以除去催化剂,得到富氢的碳纳米线(HCNW)。
样品标记为HCNW-1,其微观结构如图1和图2所示。
图3中,各衍射峰位置和相对强度均与JPCDS卡片(#38-0500)相吻合,表明产物为HCNW-1。
图4-6分别为样品的FTIR、MAS-ss-NMR、EA谱图,其结果表明HCNW样品中含有碳、氢和氧元素。
将制得的HCNW-1富氢碳材料与导电剂和粘结剂按8:1:1制作成电极,并与锂片组装成半电池,进行性能测试。其在0.1, 0.25, 0.5, 1.0 and 2.5 A/g电流密度下的容量分别为1144.2, 952.2, 752, 621.3 and 471.8 mAh/g;且在1.0 A/g电流密度下进行了3000次循环,可达到94.2%的容量保持率,具有出色的倍率和循环性能。
将制得的HCNW-1富氢碳材料与导电剂和粘结剂按8:1:1制作成电极,并与钠片组装成半电池,进行性能测试。其在0.1, 0.25, 0.5, 1.0 and 2.5 A/g电流密度下的容量分别为362.5, 286.2, 241.4, 203.7, and 145.9 mAh/g;且在1.0 A/g电流密度下进行了3000次循环,可达到89.75%的容量保持率,具有出色的倍率和循环性能,如图7所示。
将制得的HCNW-1预锂/钠化后制作成锂/钠离子电容器,进行性能测试。二者均具有较高的能量密度/功率密度(锂离子电容器:151.2 Wh/kg / 28.4 kW/kg;钠离子电容器:100.5 Wh/kg / 18.6 kW/kg)。在1.0 A/g电流密度下进行了3000次循环,锂离子电容器(LIC)具有82.16%的容量保持率,相同条件下,钠离子电容器(SIC)具有83%的容量保持率,并具有较高的库仑效率,循环过程中性能稳定性较好,如图8所示。
实施例2
一种富氢碳材料的制备方法,包括如下步骤:
A、在连续磁力搅拌下,将2 g聚合前体海藻酸钠(SA)溶于100 mL去离子水(DI)中,形成质量分数为2%的水溶液,标记为溶液A;
B、将1.5 g的无水氯化铁FeCl3溶解在100 mL去离子水形成质量分数为1.5%的水溶液,标记为溶液B;
C、在磁力搅拌下,将溶液A缓慢加入溶液B中,得到交联的海藻酸铁(IA)微凝胶珠,通过使用冷冻干燥机将洗涤的IA水凝胶珠粒冷冻干燥以蒸发水分;
D、将冷冻干燥的产物在Ar气氛下在水平管式炉中碳化2小时,碳化温度为700 ℃,将产物用1M盐酸(30%)处理以除去催化剂,得到富氢的碳纳米线(HCNW)。
样品标记为HCNW-1.5。
将本实施例制得的HCNW-1.5富氢碳材料与导电剂和粘结剂按8:1:1制作成电极,并与锂片组装成半电池,进行性能测试。在0.1 A/g电流密度下的可逆容量为781.3 mAh/g。
实施例3
一种富氢碳材料的制备方法,包括如下步骤:
A、在连续磁力搅拌下,将2 g聚合前体海藻酸钠(SA)溶于100 mL去离子水(DI)中,形成质量分数为2%的水溶液,标记为溶液A;
B、将2 g的无水氯化铁FeCl3溶解在100 mL去离子水形成质量分数为2%的水溶液,标记为溶液B;
C、在磁力搅拌下,将溶液A缓慢加入溶液B中,得到交联的海藻酸铁(IA)微凝胶珠,通过使用冷冻干燥机将洗涤的IA水凝胶珠粒冷冻干燥以蒸发水分;
D、将冷冻干燥的产物在Ar气氛下在水平管式炉中碳化2小时,碳化温度为800 ℃,将产物用1M盐酸(30%)处理以除去催化剂,得到富氢的碳纳米线(HCNW)。
样品标记为HCNW-2。
从图6的元素分析(EA)显示,三个实施例所得HCNW样品都含有H、C、O三种元素,且三份HCNW样品的H / C原子比都约为0.5,而其O / C原子比(O含量)随Fe3 +的浓度增加而增加。
将本实施例制得的HCNW-2富氢碳材料与导电剂和粘结剂按8:1:1制作成电极,并与锂片组装成半电池,进行性能测试。在0.1 A/g电流密度下的可逆容量为669.9 mAh/g。
实施例4
一种富氢碳材料的制备方法,包括如下步骤:
A、在连续磁力搅拌下,将2 g聚合前体羧甲基纤维素钠(CMC)溶于100 mL去离子水(DI)中,形成质量分数为2%的水溶液,标记为溶液A;
B、将1 g的无水氯化铁FeCl3溶解在100 mL去离子水形成质量分数为1%的水溶液,标记为溶液B;
C、在缓慢的磁力搅拌下,将溶液A缓慢加入溶液B中,得到交联的羧甲基纤维素铁微凝胶珠,通过使用冷冻干燥机将洗涤的水凝胶珠冷冻干燥以蒸发水分;
D、将冷冻干燥的产物在Ar气氛下在水平管式炉中碳化2.5小时,碳化温度为700℃,将产物用1M盐酸(30%)处理以除去催化剂,得到多孔富氢碳材料。
将本实施例制得的多孔富氢碳材料与导电剂和粘结剂按8:1:1制作成电极,并与钠片组装成半电池,进行电化学性能测试。在2.5 A/g电流密度下进行了10000次循环,达到97.1%的容量保持率,具有出色的倍率和循环性能。
将本实施例制得的多孔富氢碳材料预锂/钠化后制作成钠离子电容器,进行性能测试,展现出较高的能量密度/功率密度(122 Wh/kg / 17.6kW/kg)。在1.0 A/g电流密度下进行10000次循环后,容量保持率为95.7%,具有高的库仑效率和循环稳定性能。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (6)
1.一种富氢碳材料的制备方法,其特征在于,包括如下步骤:
A. 碳源溶于去离子水中配制成质量分数为2~10%的溶液, 标记为溶液A,其中所述碳源为海藻酸钠、羧甲基纤维素钠或生物油;
B. 催化剂溶解在去离子水配制成质量分数为1~5%的溶液, 标记为溶液B,其中所述催化剂为氯化铁、氯化锌或氯化钠;
C. 将A溶液滴加到B溶液中,搅拌下充分反应后,洗涤、冻干;
D. 干燥产物于惰性气氛中600~1000℃碳化1~5 h,酸洗,即得。
2.根据权利要求1所述富氢碳材料的制备方法,其特征在于:步骤C中所述冻干,其温度-100~-20℃,冻干时间12~72 h。
3.根据权利要求1所述富氢碳材料的制备方法,其特征在于:步骤D中所述惰性气体为氩气或氮气。
4.根据权利要求1所述富氢碳材料的制备方法,其特征在于:步骤D中所述酸洗,所用的溶液为质量分数为30%的盐酸溶液或硫酸溶液。
5.根据权利要求1所述富氢碳材料的制备方法,其特征在于:步骤D中所述碳化,所用设备为管式炉或箱式炉,升温速率为2~15℃·min−1。
6.一种根据权利要求1-5任一所述方法制备得到的富氢碳材料的应用,其特征在于:将其应用于锂/钠/钾离子电池或电容器领域。
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