CN114944479B - 石墨烯复合钾硅共掺杂磷酸钒钠的复合材料及制备和应用 - Google Patents
石墨烯复合钾硅共掺杂磷酸钒钠的复合材料及制备和应用 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 115
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 73
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KMNWCNNLFBCDJR-UHFFFAOYSA-N [Si].[K] Chemical compound [Si].[K] KMNWCNNLFBCDJR-UHFFFAOYSA-N 0.000 title description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 56
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000011591 potassium Substances 0.000 claims abstract description 55
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 51
- 239000010703 silicon Substances 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011734 sodium Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 28
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 19
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 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 abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 229910004283 SiO 4 Inorganic materials 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 239000006183 anode active material Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000011056 performance test Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 55
- 239000000243 solution Substances 0.000 description 39
- 239000000463 material Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
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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
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- H01M4/362—Composites
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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
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
- C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
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Abstract
本发明公开了一种石墨烯复合钾与硅共掺杂磷酸钒钠的复合材料。本发明还公开了一种石墨烯复合钾与硅共掺杂磷酸钒钠的复合材料的制备方法,包括以下步骤:将钒源、碳源、钠源、硅源、钾源和磷源依次溶解在去离子水中,采用水热法制备凝胶状的前驱体,将前驱体与石墨烯混合,搅拌,干燥,研磨,煅烧,获得纳米级Na3‑xKxV2(PO4)3‑y(SiO4)y@rGO颗粒。本发明以K+部分取代磷酸钒钠中的Na位,以Si4+部分取代磷酸钒钠中的P位,实现对磷酸钒钠进行双掺杂,不仅可以增强结构的稳定性,扩大钠离子迁移的通道,还可以提高磷酸钒钠的导电性。同时本发明的复合材料在电化学性能测试过程中表现出优异的倍率性能和循环性能。
Description
技术领域
本发明涉及纳米材料与电化学技术领域。更具体地说,本发明涉及一种石墨烯复合钾硅共掺杂磷酸钒钠的复合材料及制备和应用。
背景技术
电池作为一种绿色储能器件备受关注,其中锂离子电池(LIBs)由于其高安全性、高能量密度、长寿命等优点已经广泛应用于日常生活当中。然而随着对LIBs需求量日益增大以及地球中锂资源的匮乏,LIBs已经无法满足不断增长的市场需求,开发高性能电池代替LIBs是十分必要且重要的,钠离子电池(SIBs)也成为能量存储和转换领域的研究热点。钠具有与锂相似的理化性质,且在地球上的丰富度远远高于锂元素。然而,较大钠离子半径在电池充放电过程中存在脱嵌困难并影响主体材料的结构稳定性,限制了它的应用和发展。
磷酸钒钠作为聚阴离子中的代表,拥有高度开放的三维NASICON结构以及大容量和易于制备的优点,而引起了广大研究人员的研究兴趣。磷酸钒钠拥有高热稳定性、高功率密度,被认为有希望成为SIBs的候选者。然而,它固有的较低的电导率限制了它的应用。
发明内容
本发明的一个目的是解决至少上述问题,并提供至少后面将说明的优点。
本发明还有一个目的是提供一种石墨烯复合钾与硅共掺杂磷酸钒钠的复合材料,通过离子掺杂和石墨烯复合两种手段来提高其导电性,本发明以K+部分取代磷酸钒钠中的Na位,以Si4+部分取代磷酸钒钠中的P位,实现对磷酸钒钠进行双掺杂,不仅可以增强结构的稳定性,扩大钠离子迁移的通道,还可以提高磷酸钒钠的导电性。本发明还有一个目的是提供一种石墨烯复合钾与硅共掺杂磷酸钒钠的复合材料的制备方法,通过水热法将石墨烯与钾、硅共掺杂的磷酸钒钠进行复合,进一步提高磷酸钒钠的的导电性,以获得拥有高性能的磷酸钒钠正极材料,以使其成为钠离子电池的潜在应用材料。
为了实现根据本发明的这些目的和其它优点,提供了一种石墨烯复合钾、硅共掺杂磷酸钒钠的复合材料,所述复合材料的化学式为Na3-xKxV2(PO4)3-y(SiO4)y@rGO(0<x<1,0<y<0.2)。
优选的是,所述复合材料的颗粒尺寸为100-500nm。
本发明提供一种石墨烯复合钾、硅共掺杂磷酸钒钠的复合材料的制备方法,包括以下步骤:将钒源、碳源、钠源、硅源、钾源和磷源依次溶解在去离子水中,采用水热法制备凝胶状的Na3-xKxV2(PO4)3-y(SiO4)y(0<x<1,0<y<0.2)前驱体,将前驱体与石墨烯混合,搅拌,干燥,研磨,煅烧,获得纳米级Na3-xKxV2(PO4)3-y(SiO4)y@rGO(0<x<1,0<y<0.2)颗粒。
具体的是,所述钒源、所述钠源、所述硅源、所述钾源和所述磷源的摩尔比例为2:3-x:y:x:3-y,其中0<x<1,0<y<0.2。
具体的是,所述钒源和所述碳源的摩尔比例为1:1~2;
所述前驱体与所述石墨烯混合后,所述石墨烯的含量为1~5mg/mL。
具体的是,所述钒源为三异酰丙酮化钒或偏钒酸铵中的至少一种;
所述碳源为草酸或柠檬酸中的至少一种;
所述钠源为碳酸钠或碳酸氢钠中的至少一种;
所述硅源为硅酸钠或原硅酸四乙酯中的至少一种;
所述钾源为碳酸钾或磷酸二氢钾中的至少一种;
所述磷源为磷酸二氢铵。
具体的是,所述水热法的反应温度为150~200℃、反应时间为15~30h。
具体的是,所述干燥的温度为60~120℃、时间为3~10h。
具体的是,所述煅烧的设备为管式炉;
所述煅烧的氛围为Ar/H2或是N2/H2;
所述煅烧分段进行,第一段温度为350~500℃、时间为3~5h,第二段温度为600-900℃、时间为6-10h。
本发明提供一种石墨烯复合钾、硅共掺杂磷酸钒钠的复合材料及其制备方法制备得到的石墨烯复合钾、硅共掺杂磷酸钒钠的复合材料在制备钠离子电池正极活性材料的应用。
相比于现有技术,本发明至少包括以下有益效果:
本发明制备的石墨烯复合钾、硅掺杂磷酸钒钠复合材料,通过双离子掺杂,有效地提高了材料导电性,扩大了离子迁移通道,增强了结构稳定性;与石墨烯进行复合,进一步提高了磷酸钒钠的导电性。将其应用在钠离子电池正极材料时,其电化学性能表现优异。
利用水热法,将钒源、钠源、硅源、钾源和磷源按顺序加入溶液中,有利于与碳源进行更好的络合反应,形成更好的三维网络结构的凝胶,最后成功合成了石墨烯复合钾、硅共掺杂磷酸钒钠材料。
本发明工艺简单,符合绿色化学的要求,对设备要求低,有利于钠离子电池的市场化应用。
该复合材料作为钠离子正极材料,电压区间在2.5~4.0V,在0.5C、1C、5C、10C、16C、20C和40C倍率下进行恒电流充放电测试,其放电比容量分别可达115、110、100、94、89、86和113mAh g-1,表现出优异的倍率性能。
在0.5C下循环,首圈比容量高达118.8mAh g-1,首圈库伦效率为94.9%,在20C高倍率下进行充放电,循环1000次后,放电比容量为69.59mAh g-1,容量保持率为76.8%,表现出优异的循环性能和长寿命,是高功率、高能量密度离子电池的潜在应用材料。
本发明的其它优点、目标和特征将部分通过下面的说明体现,部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。
附图说明
图1是本发明实施例1的石墨烯复合钾、硅共掺杂磷酸钒钠复合材料与对比例1的石墨烯复合磷酸钒钠复合材料的结构示意图;
图2是本发明实施例1的石墨烯复合钾、硅共掺杂磷酸钒钠复合材料的XRD图;
图3是本发明实施例1的石墨烯复合钾、硅共掺杂磷酸钒钠复合材料的TEM图;
图4是本发明实施例1的石墨烯复合钾、硅共掺杂磷酸钒钠复合材料的EDSmapping图;
图5是本发明实施例1的石墨烯复合钾、硅共掺杂磷酸钒钠复合材料在0.5C低倍率下的电池循环曲线图;
图6是本发明实施例1的石墨烯复合钾、硅共掺杂磷酸钒钠复合材料在20C高倍率下的电池循环曲线图;
图7是本发明实施例1的石墨烯复合钾、硅共掺杂磷酸钒钠复合材料与对比例1的石墨烯复合磷酸钒钠复合材料的倍率性能对比图;
图8是本发明实施例1的石墨烯复合钾、硅共掺杂磷酸钒钠复合材料与对比例1的石墨烯复合磷酸钒钠复合材料的电化学阻抗谱对比图。
具体实施方式
下面结合实施例对本发明做进一步的详细说明,以令本领域技术人员参照说明书文字能够据以实施。
需要说明的是,下述实施方案中所述实验方法,如无特殊说明,均为常规方法,所述试剂和材料,如无特殊说明,均可从商业途径获得。
<实施例1>
石墨烯复合钾、硅共掺杂磷酸钒钠复合材料的制备方法,包括如下步骤:
(1)将4mmol NH4VO3加入到一定量的去离子水中,70℃水浴条件下搅拌15min使其溶解;
(2)将6mmol C2H2O4加入到步骤(1)所得的溶液中,水浴条件下搅拌15min使其溶解;
(3)将2.7mmol Na2CO3加入到步骤(2)所得的溶液中,水浴条件下搅拌15min使其溶解;
(4)将0.2mmol Na2SiO3加入到步骤(3)所得的溶液中,水浴条件下搅拌15min使其溶解;
(5)将0.1mmol K2CO3加入到步骤(4)所得的溶液中,水浴条件下搅拌15min使其溶解;
(6)将5.8mmol NH4H2PO4加入到步骤(5)所得的溶液中,水浴条件下搅拌15min使其溶解;
(7)将步骤(6)所得的溶液转移至聚四氟乙烯内胆中,装配反应釜,放置在鼓风干燥箱内,190℃水热反应20h;
(8)将步骤(7)得到的凝胶转移至烧杯中,加入48mL 2mg/mL石墨烯溶液,搅拌12h使其均匀混合;
(9)将步骤(8)得到的溶液放置在鼓风干燥箱内,120℃干燥6h,将溶液中的水除去,得到的黑色固体在研钵中研磨成粉末;
(10)将步骤(9)中研磨所得的黑色粉末置于管式炉中,在Ar/H2的气氛下400℃煅烧4h,700℃下煅烧8h,即得到石墨烯复合钾、硅共掺杂磷酸钒钠复合材料。所述复合材料的颗粒尺寸为100-500nm。
以本实例产物石墨烯复合钾、硅共掺杂磷酸钒钠复合材料为例,其微观结构如图1所示。其结构有X-射线衍射仪(XRD)确定,如图2所示,XRD表明,石墨烯复合钾、硅共掺杂磷酸钒钠复合材料的特征峰能够很好地与三方晶系Na3V2(PO4)3晶体的标准卡片(PDF:#53-0018)匹配,证明Na3V2(PO4)3为主要物相且无其他杂相。图3为SEM图,由图可知,在SEM下可以很清楚的看出材料呈现片状,证明了石墨烯片的存在,有利于提高材料的导电性。图4为本实施例的石墨烯复合钾、硅共掺杂磷酸钒钠复合材料的EDS mapping图,通过mapping图可以看出K、Si掺杂进晶体结构中,且各个元素分布均匀。
本实施例制备的石墨烯复合钾、硅共掺杂磷酸钒钠复合材料应用在钠离子电池正极活性材料,钠离子电池的制备方法其余步骤与通常的制备方法相同。钠离子电池正极电极片的制备方法如下,采用以石墨烯复合钾、硅共掺杂磷酸钒钠材料作为活性物质,SuperP作为导电剂,聚偏二氟乙烯(PVDF)为粘结剂,活性物质、Super P和PVDF的质量比为7:2:1,将它们按比例充分混合后,再将其均匀涂覆在铝箔上,在120℃的烘箱内活化12h,用冲孔机冲成11mm的电极片后备用。
以1mol/L的NaClO4、体积比1:1的碳酸乙烯酯(EC)和碳酸二甲酯(DMC)、质量分数为5%的氟代碳酸乙烯酯(FEC)的混合溶液用作电解液,本实施例制备的电极片作为正极,自制的钠片为负极,玻璃纤维为隔膜,LIR2025型不锈钢为电池外壳组装成扣式钠离子电池。
以本实例制备的石墨烯复合钾、硅共掺杂磷酸钒钠复合材料作为钠离子电池正极活性材料为例,如图5所示,该材料在0.5C下进行测试,首圈比容量高达118.9mAh g-1,首圈库伦效率高达94.9%,在此之后的循环中,库伦效率接近100%,循环100圈后,放电比容量可达109.8mAh g-1,表现出优异的循环性能。如图6所示,该材料在20C大倍率下进行恒电流充放电测试,循环1000次后,放电比容量仍达69.59mAh g-1,具有良好的循环性能和长寿命性能。如图7所示,该材料分别在0.5C、1C、5C、10C、16C、20C、40C的倍率下进行恒电流充放电测试,其放电比容量分别为115、110、100、94、89、86和76mAh g-1,表现出优异的倍率性能。上述性能表明石墨烯复合钾、硅共掺杂磷酸钒钠材料具有优异的高倍率特性和循环性能,是高功率、长寿命钠离子电池的潜在应用材料。
<实施例2>
石墨烯复合钾、硅共掺杂磷酸钒钠复合材料的制备方法,包括如下步骤:
(1)将4mmol C15H21O6V加入到一定量的去离子水中,70℃水浴条件下搅拌15min使其溶解;
(2)将8mmol C2H2O4加入到步骤(1)所得的溶液中,水浴条件下搅拌15min使其溶解;
(3)将4.6mmol NaHCO3加入到步骤(2)所得的溶液中,水浴条件下搅拌15min使其溶解;
(4)将0.4mmol Na2SiO3加入到步骤(3)所得的溶液中,水浴条件下搅拌15min使其溶解;
(5)将0.6mmol KH2PO4加入到步骤(4)所得的溶液中,水浴条件下搅拌15min使其溶解;
(6)将5mmol NH4H2PO4加入到步骤(5)所得的溶液中,水浴条件下搅拌15min使其溶解;
(7)将步骤(6)所得的溶液转移至聚四氟乙烯内胆中,装配反应釜,放置在鼓风干燥箱内,160℃水热反应25h;
(8)将步骤(7)得到的凝胶转移至烧杯中,加入48mL 2mg/mL石墨烯溶液,搅拌12h使其均匀混合;
(9)将步骤(8)得到的溶液放置在鼓风干燥箱内,100℃干燥7h,将溶液中的水除去,得到的黑色固体在研钵中研磨成粉末;
(10)将步骤(9)中研磨所得的黑色粉末置于管式炉中,在Ar/H2的气氛下450℃煅烧5h,800℃下煅烧7h,即得到石墨烯复合钾、硅共掺杂磷酸钒钠复合材料。
以本实例制备的石墨烯复合钾、硅掺杂磷酸钒钠复合材料为钠离子电池正极材料为例,在0.5C的小倍率下进行充放电测试,循环100次后,放电比容量仍可达97.8mAh g-1,具有良好的电化学性能。
<实施例3>
石墨烯复合钾、硅共掺杂磷酸钒钠复合材料的制备方法,包括如下步骤:
(1)将4mmol NH4VO3加入到一定量的去离子水中,70℃水浴条件下搅拌15min使其溶解;
(2)将4mmol C6H8O7加入到步骤(1)所得的溶液中,水浴条件下搅拌15min使其溶解;
(3)将2.6mmol Na2CO3加入到步骤(2)所得的溶液中,水浴条件下搅拌15min使其溶解;
(4)将0.3mmol原硅酸四乙酯加入到步骤(3)所得的溶液中,水浴条件下搅拌15min使其溶解;
(5)将0.8mmol KH2PO4加入到步骤(4)所得的溶液中,水浴条件下搅拌15min使其溶解;
(6)将4.9mmol NH4H2PO4加入到步骤(5)所得的溶液中,水浴条件下搅拌15min使其溶解;
(7)将步骤(6)所得的溶液转移至聚四氟乙烯内胆中,装配反应釜,放置在鼓风干燥箱内,180℃水热反应24h;
(8)将步骤(7)得到的凝胶转移至烧杯中,加入48mL 2mg/mL石墨烯溶液,搅拌12h使其均匀混合;
(9)将步骤(8)得到的溶液放置在鼓风干燥箱内,100℃干燥6h,将溶液中的水除去,得到的黑色固体在研钵中研磨成粉末;
(10)将步骤(9)中研磨所得的黑色粉末置于管式炉中,在Ar/H2的气氛下500℃煅烧4h,750℃下煅烧10h,即得到石墨烯复合钾、硅共掺杂磷酸钒钠复合材料。
以本实例制备的石墨烯复合钾、硅掺杂磷酸钒钠复合材料为钠离子电池正极材料为例,在0.5C的小倍率下进行充放电测试,循环100次后,放电比容量仍可达96.0mAh g-1,具有良好的电化学性能。
<对比例1>
石墨烯复合磷酸钒钠复合材料的制备方法,包括以下步骤:
(1)将4mmol NH4VO3加入到一定量的去离子水中,70℃水浴条件下搅拌15min使其溶解;
(2)将6mmol C2H2O4加入到步骤(1)所得的溶液中,水浴条件下搅拌15min使其溶解;
(3)将3mmol Na2CO3加入到步骤(2)所得的溶液中,水浴条件下搅拌15min使其溶解;
(4)将6mmol NH4H2PO4加入到步骤(3)所得的溶液中,水浴条件下搅拌15min使其溶解;
(5)将步骤(4)所得的溶液倒入聚四氟乙烯内胆中,在190℃下水热反应20h;
(6)将步骤(5)得到的凝胶倒入烧杯中,加入48mL 2mg/L石墨烯溶液,搅拌12h使其均匀混合;
(7)将步骤(6)得到的溶液放置在鼓风干燥箱内,120℃干燥6h,将溶液中的水蒸发;
(8)将步骤(7)所得黑色粉末置于管式炉中,在Ar/H2的氛围下分段煅烧,第一段在温度为400℃,煅烧4h,第二段在温度为700℃,煅烧8h,即得到黑色粉末状的石墨烯复合磷酸钒钠复合材料。
以本实例产物为例,该复合材料为纳米颗粒,其材料的颗粒尺寸为50-100nm。
以本实例制备的石墨烯复合磷酸钒钠复合材料为钠离子电池正极材料为例,在0.5C的小倍率下进行充放电测试,循环100次后,放电比容量仍可达93.5mAh g-1,具有良好的电化学性能。
由图7可知,实施例1的石墨烯复合钾、硅共掺杂磷酸钒钠复合材料相比于对比例1的石墨烯复合磷酸钒钠复合材料,其倍率性能更好。
图8是本发明实施例1的石墨烯复合钾、硅共掺杂磷酸钒钠复合材料与对比例1的石墨烯复合磷酸钒钠复合材料的电化学阻抗谱对比图。由图8可知,实施例1的复合材料的电化学阻抗性能明显优于对比例1的复合材料。
尽管本发明的实施方案已公开如上,但其并不仅仅限于说明书和实施方式中所列运用,它完全可以被适用于各种适合本发明的领域,对于熟悉本领域的人员而言,可容易地实现另外的修改,因此在不背离权利要求及等同范围所限定的一般概念下,本发明并不限于特定的细节和这里示出与描述的实施例。
Claims (4)
1.一种石墨烯复合钾与硅共掺杂磷酸钒钠的复合材料,其特征在于,所述复合材料的化学式为Na3-xKxV2(PO4)3-y(SiO4)y@rGO,其中,0<x<1,0<y<0.2;所述复合材料的颗粒尺寸为100-500 nm;
所述复合材料通过以下方法制备:
将钒源、碳源、钠源、硅源、钾源和磷源依次溶解在去离子水中,采用水热法制备凝胶状的Na3-xKxV2(PO4)3-y(SiO4)y前驱体,将前驱体与石墨烯混合,搅拌,干燥,研磨,煅烧,获得纳米级Na3-xKxV2(PO4)3-y(SiO4)y@rGO颗粒;所述水热法的反应温度为150~200℃、反应时间为15~30 h;所述钒源、所述钠源、所述硅源、所述钾源和所述磷源的摩尔比例为2 : 3-x: y: x:3-y;所述钒源和所述碳源的摩尔比例为1:1~2;所述前驱体与所述石墨烯混合后,所述石墨烯的含量为1~5 mg/mL;
所述钒源为三异酰丙酮化钒或偏钒酸铵中的至少一种;
所述碳源为草酸或柠檬酸中的至少一种;
所述钠源为碳酸钠或碳酸氢钠中的至少一种;
所述硅源为硅酸钠或原硅酸四乙酯中的至少一种;
所述钾源为碳酸钾或磷酸二氢钾中的至少一种;
所述磷源为磷酸二氢铵;
所述煅烧的设备为管式炉;
所述煅烧的氛围为Ar/H2或是N2/H2;
所述煅烧分段进行,第一段温度为350~500℃、时间为3~5 h,第二段温度为600-900℃、时间为6-10 h。
2.如权利要求1所述的石墨烯复合钾与硅共掺杂磷酸钒钠的复合材料的制备方法,其特征在于,包括以下步骤:将钒源、碳源、钠源、硅源、钾源和磷源依次溶解在去离子水中,采用水热法制备凝胶状的Na3-xKxV2(PO4)3-y(SiO4)y (0<x<1,0<y<0.2)前驱体,将前驱体与石墨烯混合,搅拌,干燥,研磨,煅烧,获得纳米级Na3-xKxV2(PO4)3-y(SiO4)y@rGO (0<x<1,0<y<0.2)颗粒;所述水热法的反应温度为150~200℃、反应时间为15~30 h;
所述钒源、所述钠源、所述硅源、所述钾源和所述磷源的摩尔比例为2 : 3-x: y: x :3-y;
所述钒源和所述碳源的摩尔比例为1:1~2;
所述前驱体与所述石墨烯混合后,所述石墨烯的含量为1~5 mg/mL;
所述钒源为三异酰丙酮化钒或偏钒酸铵中的至少一种;
所述碳源为草酸或柠檬酸中的至少一种;
所述钠源为碳酸钠或碳酸氢钠中的至少一种;
所述硅源为硅酸钠或原硅酸四乙酯中的至少一种;
所述钾源为碳酸钾或磷酸二氢钾中的至少一种;
所述磷源为磷酸二氢铵;
所述煅烧的设备为管式炉;
所述煅烧的氛围为Ar/H2或是N2/H2;
所述煅烧分段进行,第一段温度为350~500℃、时间为3~5 h,第二段温度为600-900℃、时间为6-10 h。
3.如权利要求2所述的石墨烯复合钾与硅共掺杂磷酸钒钠的复合材料的制备方法,其特征在于,所述干燥的温度为60~120℃、时间为3~10 h。
4.如权利要求1所述的石墨烯复合钾与硅共掺杂磷酸钒钠的复合材料或如权利要求2或3所述的制备方法制备得到的石墨烯复合钾与硅共掺杂磷酸钒钠的复合材料在制备钠离子电池正极活性材料的应用。
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