CN115448289A - 一种氧氟共掺杂硬碳负极材料及其制备方法与应用 - Google Patents
一种氧氟共掺杂硬碳负极材料及其制备方法与应用 Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 50
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- UOBPHQJGWSVXFS-UHFFFAOYSA-N [O].[F] Chemical compound [O].[F] UOBPHQJGWSVXFS-UHFFFAOYSA-N 0.000 title abstract description 25
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 43
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011737 fluorine Substances 0.000 claims abstract description 42
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 20
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 229910052760 oxygen Inorganic materials 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000001509 sodium citrate Substances 0.000 claims description 13
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001508 potassium citrate Substances 0.000 claims description 3
- 229960002635 potassium citrate Drugs 0.000 claims description 3
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 3
- 235000011082 potassium citrates Nutrition 0.000 claims description 3
- YPSNMKHPDJVGEX-UHFFFAOYSA-L potassium;sodium;3-carboxy-3-hydroxypentanedioate Chemical compound [Na+].[K+].OC(=O)CC(O)(C([O-])=O)CC([O-])=O YPSNMKHPDJVGEX-UHFFFAOYSA-L 0.000 claims description 3
- 229960001790 sodium citrate Drugs 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011641 cupric citrate Substances 0.000 claims description 2
- 235000019855 cupric citrate Nutrition 0.000 claims description 2
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- 239000004337 magnesium citrate Substances 0.000 claims description 2
- 229960005336 magnesium citrate Drugs 0.000 claims description 2
- 235000002538 magnesium citrate Nutrition 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- STDMRMREKPZQFJ-UHFFFAOYSA-H tricopper;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O STDMRMREKPZQFJ-UHFFFAOYSA-H 0.000 claims description 2
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 14
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
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- 239000003575 carbonaceous material Substances 0.000 description 8
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 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 description 3
- 239000006229 carbon black Substances 0.000 description 3
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- 239000007772 electrode material Substances 0.000 description 3
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- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 230000007847 structural defect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
本发明属于钾离子电池材料技术领域,具体涉及一种氧氟共掺杂硬碳负极材料及其制备方法与应用。本发明采用柠檬酸盐与氟源制备得到的氧氟共掺杂硬碳负极材料具有丰富的缺陷位点及孔道结构,具有较大的比表面积,作为负极材料时,有利于提高钾离子电池的倍率性能及循环稳定性;所采用的原料来源广泛、廉价易得;制备方法简单、条件温和,有利于大规模生产。
Description
技术领域
本发明属于钾离子电池材料技术领域。更具体地,涉及一种氧氟共掺杂硬碳负极材料及其制备方法与应用。
背景技术
锂离子电池作为一种商业化的储能系统已经主导了储能市场。然而,由于锂源储量有限以及地理分布不均,导致锂离子电池的成本不断升高,严重影响锂离子电池的应用。因此研究者将重点转向其他资源丰富、性能优良的替代电池技术,如镁离子电池、铝离子电池、钠离子电池、钾离子电池等。其中,新兴的钾离子电池具有许多优势,如钾离子电池导电性、柔韧性好,且钾在地壳中的含量丰富、成本低且环境友好,这引起了广大研究者们研究兴趣。对于钾离子电池而言,负极材料对钾离子电池的性能具有较大影响,碳材料是钾离子电池中常用的一种负极材料,其具有绿色环保、原料廉价易得、导电性好、插层电压平台较低(≥0.2V vs K+/K)的优点,但其层间距(0.34nm)较小,使插层反应过程中动力学缓慢,并且会产生巨大的重复性体积变化,对其倍率性能及循环稳定性造成了不利的影响。如中国专利申请公开了一种氮氟原子掺杂三维多孔碳的电极材料,其具有导电性好,比容量高的优点,但其循环性能较差(循环50圈就损失20%)。
发明内容
本发明要解决的技术问题是克服现有钾离子电池负极材料循环稳定性差的缺陷和不足,提供一种氧氟共掺杂硬碳负极材料的制备方法,该方法制备出来的氧氟共掺杂硬碳负极材料具有较好的循环稳定性和较高的倍率性能。
本发明的目的是提供一种氧氟共掺杂硬碳负极材料在制备钾离子电池负极材料中的应用。
本发明的另一目的是提供氧氟共掺杂硬碳负极材料。
本发明的上述目通过以下技术方案实现:
一种氧氟共掺杂硬碳负极材料的制备方法,包括如下步骤:
将柠檬酸盐与氟源在极性溶剂中混匀,在惰性气体氛围、400~1000℃下热处理,纯化即得;
所述柠檬酸盐与氟源的质量比为1:(0.05~4)。
本发明创造性的采用简单易得的柠檬酸盐和氟源制备硬碳负极材料。柠檬酸盐中含有氧原子和碳原子,在本发明中作为氧源、碳源及原位模板剂,在热处理过程中柠檬酸盐受热分解产生大量氧和碳,氟源产生大量的氟,氧元素掺杂在碳材料中能提高氟元素掺杂的浸润性,同时提供额外的活性位点,有利于负极材料容量的提升;氧氟双杂原子掺杂可以改善负极材料的局部电子构型和结构缺陷,增强负极材料和电子的亲和力,氧氟杂原子与碳原子的化学键合可以增加负极材料的活性位点,将氧氟杂原子以间隙掺杂的方式进行掺杂,可以增大负极材料的层间距以及缓冲体积变化,从而提高负极材料的电化学性能。
同时,在热解过程中,柠檬酸盐受热分解会原位生成碱性碳酸盐,放出二氧化碳,碱性碳酸盐与二氧化碳对于碳材料具有活化作用,有利于形成微孔结构。柠檬酸盐的有机组分在热处理过程中与氟源热解形成氧氟共掺的碳层,碳层沿着柠檬酸盐热解生成的原位碳酸盐模板剂生长,聚四氟乙烯高分子链的存在,能够使得模板剂表面的碳层更为完整,用去离子水或稀酸除去碳酸盐模板后形成独特片层结构的硬碳材料,即为本申请的氧氟共掺杂硬碳负极材料。
优选地,所述氟源为聚四氟乙烯或聚偏氟乙烯。
更优选地,所述氟源为聚四氟乙烯。
优选地,所述柠檬酸盐为柠檬酸锂、柠檬酸钾、柠檬酸钠、柠檬酸钾钠、柠檬酸铁、柠檬酸铜、柠檬酸镁、柠檬酸铵或上述柠檬酸盐水合物中的一种或多种。
更优选地,所述柠檬酸盐为柠檬酸钾、柠檬酸钠或柠檬酸钾钠。
优选地,所述柠檬酸盐与氟源的质量比为1:(0.05~0.2)。
优选地,所述热处理的时间为30~360min。
更优选地,所述热处理的时间为30~120min。
优选地,所述热处理的温度为500~900℃。
优选地,所述极性溶剂为水。
更优选地,所述水为去离子水。
优选地,所述惰性气体包括氮气或氩气。
优选地,所述纯化包括清洗、干燥。
更优选地,所述清洗用稀硫酸、稀盐酸、稀硝酸或去离子水清洗。
本发明进一步保护一种氧氟共掺杂硬碳负极材料,由上述制备方法得到。
本发明进一步保护上述氧氟共掺杂硬碳负极材料在制备钾离子电池负极材料中的应用。
本发明具有以下有益效果:
本发明采用柠檬酸盐与氟源制备得到的氧氟共掺杂硬碳负极材料具有丰富的缺陷位点及孔道结构,具有较大的比表面积,作为负极材料时,有利于提高钾离子电池的倍率性能及循环稳定性;所采用的原料来源广泛、廉价易得;制备方法简单、条件温和,有利于大规模生产。
附图说明
图1为本发明实施例1制备的氧氟共掺杂硬碳负极材料在场发射扫描电子显微镜(SEM)下的微观形貌以及元素分布图(EDS)。
图2为本发明实施例1制备的氧氟共掺杂硬碳负极材料的X-射线衍射图(XRD)。
图3为本发明实施例1制备的氧氟共掺硬碳负极材料的拉曼光谱仪图。
图4为本发明实施例1制备的氧氟共掺硬碳负极材料的BET比表面积及孔径分析仪图。
图5为本发明实施例1制备的氧氟共掺硬碳负极材料在不同电流密度下的倍率性能结果图。
图6为本发明实施例1制备的氧氟共掺硬碳负极材料的首圈库伦效率及在1A·g-1电流密度下循环1000次的长循环性能结果图。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明,以下实施例所用试剂和材料均为市购。
实施例1氧氟共掺杂硬碳负极材料的制备
S1.将质量比为20:1的柠檬酸钠与聚四氟乙烯溶于去离子水中混合,干燥得前体;
S2.将步骤S1所得前体,在氮气气氛保护下以3℃/min的升温速率升至600℃后保温1h对其进行热处理得热解产物;
S3.将步骤S2所得热解产物用去离子水搅拌清洗,随后抽滤得到固体产物,反复清洗三次,干燥即得,所得材料氧掺杂量为12%,氟掺杂量为4%。
实施例2氧氟共掺杂硬碳负极材料的制备
S1.将质量比为10:1的柠檬酸钠与聚四氟乙烯溶于去离子水中混合,干燥得前体;
S2.将步骤S1所得前体,在氮气气氛保护下以3℃/min的升温速率升至500℃后保温1h对其进行热处理得热解产物;
S3.将步骤S2所得热解产物用去离子水搅拌清洗,随后抽滤得到固体产物,反复清洗三次,干燥即得。
实施例3氧氟共掺杂硬碳负极材料的制备
S1.将质量比为5:1的柠檬酸钠与聚四氟乙烯溶于去离子水中混合,干燥得前体;
S2.将步骤S1所得前体,在氮气气氛保护下以3℃/min的升温速率升至700℃后保温1h对其进行热处理得热解产物;
S3.将步骤S2所得热解产物用去离子水搅拌清洗,随后抽滤得到固体产物,反复清洗三次,干燥即得。
实施例4氧氟共掺杂硬碳负极材料的制备
S1.将质量比为1:1的柠檬酸钠与聚四氟乙烯溶于去离子水中混合,干燥得前体;
S2.将步骤S1所得前体,在氮气气氛保护下以3℃/min的升温速率升至800℃后保温1h对其进行热处理得热解产物;
S3.将步骤S2所得热解产物用去离子水搅拌清洗,随后抽滤得到固体产物,反复清洗三次,干燥即得。
对比例1氧掺杂硬碳负极材料的制备
S1.将质量比为20:1的柠檬酸钠在氮气气氛保护下以3℃/min的升温速率升至600℃后保温1h对其进行热处理得热解产物;
S2.将步骤S1所得热解产物用去离子水搅拌清洗,随后抽滤得到固体产物,反复清洗三次,即得。
与实施例1相比,步骤S1中不添加聚四氟乙烯,所得硬碳负极材料中缺陷位点较少,活性位点较少。
对比例2氧氟共掺杂硬碳负极材料的制备
S1.将质量比为10:1的柠檬酸与聚四氟乙烯溶于去离子水中混合,干燥得前体;
S2.将步骤S1所得前体,在氮气气氛保护下以3℃/min的升温速率升至500℃后保温1h对其进行热处理得热解产物;
S3.将步骤S2所得热解产物用去离子水搅拌清洗,随后抽滤得到固体产物,反复清洗三次,即得。
与实施例2相比,将实施例2中的柠檬酸钠替换成本对比例的柠檬酸,在热解过程中,柠檬酸只作为含氧碳源,分解时没有碱性碳酸盐生成,产物中孔道结构较少。
对比例3氧氟共掺杂硬碳负极材料的制备
S1.将质量比为1:5的柠檬酸钠与聚四氟乙烯溶于去离子水中混合,干燥得前体;
S2.将步骤S1所得前体,在氮气气氛保护下以3℃/min的升温速率升至600℃后保温1h对其进行热处理得热解产物;
S3.将步骤S2所得热解产物用稀盐酸搅拌清洗,随后抽滤得到固体产物,反复清洗三次,干燥即得。
与实施例1的区别仅在于,将柠檬酸钠与聚四氟乙烯的质量比改为1:5。
实验例1结构表征
扫描电子显微镜测试:将实施例1制备得到氧氟共掺杂硬碳负极材料进行扫描电子显微镜(SEM)测试。结果如图1所示,制备得到氧氟共掺杂硬碳负极材料为蜂窝状的开放式片层,氧元素、氟元素均匀掺杂在碳材料中,且呈现出多孔的特性。
X射线衍射测试:使用X射线衍射仪对实施例1制备得到氧氟共掺杂硬碳负极材料进行物相分析。结果如图2所示,在2θ为21.2°和44.4°附近出现了两个宽的衍射峰,分别对应氧氟共掺杂硬碳负极材料的(002)晶面峰和(101)晶面峰,但两个衍射峰较宽,说明所制备材料无序程度较高,所述产物为无定形态。
拉曼光谱测试:将实施例1制备得到氧氟共掺杂硬碳负极材料使用拉曼光谱仪进行化学组成分析。结果如图3所示,在1350cm-1和1590cm-1附近出现属于氧氟共掺杂硬碳负极材料的两个标准峰(D峰与G峰),峰形较宽不尖锐,其ID/IG为0.99,证明材料中所含缺陷位点较多,石墨化程度较低。
BET比表面积测试:将实施例1制备得到氧氟共掺杂硬碳负极材料使用比表面积及孔径分析仪进行BET比表面积测试。结果如图4所示,所得氧氟共掺杂硬碳负极材料比表面较大,为184.3722m2/g,总孔体积为0.5383mL/g,平均孔直径为11.6786nm。
实验例2电化学性能测试
所述氧氟共掺杂硬碳负极材料应用于钾离子半电池,可利用现有技术手段组装,CR2032扣式电池壳作为外壳,金属钾片作为负极,负载所述氧氟共掺杂硬碳负极材料、炭黑及羧甲基纤维素钠铜箔作为正极(氧氟共掺杂硬碳负极材料、炭黑及羧甲基纤维素钠的质量比为8:1:1),1M的双氟磺酰亚胺钾(KFSI)酯类电解液(碳酸乙烯酯与碳酸二乙酯体积比为1:1的复合溶剂)作为电解液,玻璃纤维隔膜作为电池隔膜。
所述氧氟共掺杂硬碳负极材料作为钾离子半电池负极,可使用现有技术手段测试其电化学性能。
各实施例及对比例制备得到的硬碳负极材料作为钾离子电池负极时的起始比容量及在1A·g-1电流密度下循环1000圈后平均每圈容量衰减率如表1所示:表1:各实施例及对比例应用于钾离子电池负极时在1A·g-1电流密度下的起始比容量和循环1000圈后平均每圈容量衰减率
从表1可以看出,各实施例制备得到的氧氟共掺杂硬碳负极材料电化学性能均优于对比例,其中实施例1所得氧氟共掺杂硬碳负极材料性能最好,起始比容量达到181.4mAh·g-1,循环1000圈后平均每圈容量衰减率仅为0.012%。
对比例1选用柠檬酸钠直接碳化,没有加入含F的有机化合物,在热解过程中没有F原子进行掺杂,因此,所得碳材料的缺陷位点较少,活性位点较少,起始比容量不高,仅为50mAh·g-1。在电化学循环过程中,对比例1与炭黑及羧甲基纤维素钠混合后磨成的浆料在铜箔表面附着性较差,易从铜箔表面脱落,造成接触不良,因此循环稳定性不佳,1A·g-1电流密度下循环50圈后即发生不可逆失活。
对比例2选用柠檬酸与聚四氟乙烯反应,在反应过程中,柠檬酸仅仅作为含氧碳源,热解过程中没有碱性碳酸盐生成,无法在碳材料中形成孔道结构,亦无法对碳材料产生活化作用,形成微孔,使得电解液无法充分浸润,内部材料与电解液接触性较差,影响了钾离子扩散。同时在电化学循环过程中,电极材料容易发生断裂脱落,电化学性能不佳,在循环100圈后,电极材料即发生不可逆的硬失活。
对比例3仅将柠檬酸钠与聚四氟乙烯的质量比改为1:5,其所制备得到的氧氟共掺杂硬碳负极材料的起始比容量就降低为65%,循环1000圈后平均每圈容量衰减率上升为0.037%。
实施例1中制备氧氟共掺杂硬碳负极材料作为钾离子电池负极时的倍率性能及长循环性能如图5及图6所示。由图5可以看出本发明实施例1制备的氧氟共掺杂硬碳负极材料具有良好的倍率性能及小电流循环稳定性,倍率循环完成后,在小电流(电流密度为0.1A·g-1)下继续循环70圈后,比容量没有明显下降。由图6可以看出该材料具有良好的循环稳定性,在电流密度1A·g-1下循环1000圈后(0.1A·g-1下活化三圈),比容量没有明显下降,容量保持率达到了99%。
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,其他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)
1.一种氧氟共掺杂硬碳负极材料的制备方法,其特征在于,包括如下步骤:
将柠檬酸盐与氟源在极性溶剂中混匀,在惰性气体氛围、400~1000℃下热处理,纯化即得;
所述柠檬酸盐与氟源的质量比为1:(0.05~4)。
2.根据权利要求1所述制备方法,其特征在于,所述氟源为聚四氟乙烯或聚偏氟乙烯。
3.根据权利要求1所述制备方法,其特征在于,所述柠檬酸盐为柠檬酸锂、柠檬酸钾、柠檬酸钠、柠檬酸钾钠、柠檬酸铁、柠檬酸铜、柠檬酸镁、柠檬酸铵或上述柠檬酸盐水合物中的一种或多种。
4.根据权利要求1所述制备方法,其特征在于,所述柠檬酸盐与氟源的质量比为1:(0.05~0.2)。
5.根据权利要求1所述制备方法,其特征在于,所述热处理的时间为30~360min。
6.根据权利要求1所述制备方法,其特征在于,所述热处理的温度为500~900℃。
7.根据权利要求1所述制备方法,其特征在于,所述极性溶剂为水。
8.根据权利要求1所述制备方法,其特征在于,所述惰性气体包括氮气或氩气。
9.一种氧氟共掺杂硬碳负极材料,其特征在于,由权利要求1~8任一所述制备方法得到。
10.权利要求9所述氧氟共掺杂硬碳负极材料在制备钾离子电池负极材料中的应用。
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