CN107681148B - 一种多孔无定形二氧化钛基钠离子电池及其制备方法 - Google Patents
一种多孔无定形二氧化钛基钠离子电池及其制备方法 Download PDFInfo
- Publication number
- CN107681148B CN107681148B CN201710877801.XA CN201710877801A CN107681148B CN 107681148 B CN107681148 B CN 107681148B CN 201710877801 A CN201710877801 A CN 201710877801A CN 107681148 B CN107681148 B CN 107681148B
- Authority
- CN
- China
- Prior art keywords
- ion battery
- sodium
- porous amorphous
- amorphous tio
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004408 titanium dioxide Substances 0.000 title abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920000084 Gum arabic Polymers 0.000 claims description 4
- 241000978776 Senegalia senegal Species 0.000 claims description 4
- 235000010489 acacia gum Nutrition 0.000 claims description 4
- 239000000205 acacia gum Substances 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 239000010406 cathode material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明属于一种电池材料技术领域，具体涉及一种多孔无定形二氧化钛基钠离子电池。本发明采用水热法，首先将1‑4g硫酸氧钛与20‑25ml乙醇混合搅拌后倒入装有40‑45ml浓度为10‑15 M的NaOH反应釜中，最后加入1‑2g的NaHCO3，在150‑180℃的环境下反应1‑3天后，再经离心洗涤样品并收集得到白色的多孔无定形TiO2，然后在进行钠离子电池的组装。本发明制得的钠离子电池具有较高的比容量、优异的倍率充放电性能和良好的循环稳定性，制备工艺简单，具有很好的应用前景。
Description
技术领域
本发明属于一种电池材料技术领域，具体涉及一种多孔无定形二氧化钛基钠离子电池及其制备方法。
背景技术
锂离子电池具有能量密度高、功率密度高、循环寿命长和毒性小等诸多的优点，广泛应用于手机、笔记本电脑等电子设备。钠与锂属于同一主族，具有相似的理化性质，且电池的充放电原理基本一致。与锂离子电池相比，钠离子电池具有以下特点：钠资源丰富，约占地壳元素储量的2.64%，而且价格低廉，分布广泛。从钠离子电池的充放电原理可得知，钠离子电池因缺乏合适的电极材料而制约其应用，开发性能优异的钠离子电池正负极材料是当前该领域的研究重点和热点。作为热门的负极材料二氧化钛具有高的工作电压及优异的结构稳定性，使得它作为钠离子电池负极材料具有优异的安全性能、循环和倍率性能。二氧化钛对环境友好，成本低廉、在钠离子嵌入/脱出的过程中结构稳定，在高能量储存中具有很大的发展潜力。但是TiO2作为钠离子电池负极材料，存在电子导电性和钠离子扩散性不佳的缺点，为了弥补这两点不足，本发明首次提供了一种高性能多孔无定形TiO2基钠离子电池负极材料的制备方法。
发明内容
本发明的目的在于提供一种高性能多孔无定形TiO2基钠离子电池负极材料的制备方法。
为实现上述目的，本发明采用如下技术方案：
所述无定形多孔TiO2基钠离子电池负极材料的制备，具体为：采用水热法，首先将1-4g硫酸氧钛与20-25ml乙醇混合搅拌后倒入装有40-45ml浓度为10-15 M的NaOH反应釜中，最后加入1-2g的NaHCO3，在150-180℃的环境下反应1-3天后，再经离心洗涤样品并收集得到白色的多孔无定形TiO2。
钠离子电池组装：按质量比计，无定形TiO2：乙炔黑：阿拉伯树胶 =75-80：10-15：5-10，混合研磨均匀涂在1.2cm2的铜片上做工作电极，采用金属钠片做对电极，电解质是1MNaClO4的EC+DEC(EC/DEC=1/1 V/V)溶液；电池组装在氩气保护下手套箱里进行（氧气和水分含量均低于1ppm）。
本发明的显著优点在于：利用廉价的无机钛源经过简单的水热和造孔方法就制备出了高度多孔的无定型TiO2材料，这种材料同时具有微米棒状的形貌，使其在有利于电解液接触和储存的同时兼具高的振实密度，这对于材料在电池领域的实际应用是非常关键的。目前该材料的各项优异的性能指标表明其在储能领域良好的应用前景，绝大部分指标已达到实用化级别。
附图说明
图1为本发明制得的材料和样品进行400度煅烧后的XRD分析；
图2为多孔无定形TiO2的扫描电镜分析图；
图3为多孔无定形TiO2基钠离子电池的充放电曲线；
图4为多孔无定形TiO2基钠离子电池的循环性能图。
具体实施方式
为进一步公开而不是限制本发明，以下结合实例对本发明作进一步的详细说明。
实施例1
所述无定形多孔TiO2基钠离子电池负极材料的制备，具体为：采用水热法，用1-4g硫酸氧钛与20-25ml乙醇混合搅拌后倒入装有40-45ml浓度为10-15 M的NaOH反应釜中，最后加入1-2g的NaHCO3，在150-180℃的环境下反应1-3天后，再经离心洗涤样品并收集得到白色的多孔无定形TiO2。
钠离子电池组装：按质量比计，无定形TiO2：乙炔黑：阿拉伯树胶 =75-80：10-15：5-10，混合研磨均匀涂在1.2cm2的铜片上做工作电极，采用金属钠片做对电极，电解质是1MNaClO4的EC+DEC(EC/DEC=1/1 V/V)溶液；电池组装在氩气保护下手套箱里进行（氧气和水分含量均低于1ppm）。
从图1的XRD图可知所制备的样品为无定型相的材料，为了证实材料的成分将其进行400度煅烧处理，结果证实其成分为锐钛矿TiO2；因此可推断所制备样品为无定型结构TiO2。对样品进行扫描电镜观察，发现这种无定型TiO2是由纳米棒构筑形成，长度为2-7 um，直径为300 nm-1um。扫描电镜观察它表面是有较多孔隙。用这种无定形多孔TiO2作为钠离子电池负极材料，结果表明其具有较高的比容量、优异的倍率充放电性能和良好的循环稳定性。在电流密度为0.1A g-1下进行充放电，首次充电比容量可达281mA g-1.在电流密度为1Ag-1情况下循环，其首次可逆比容量高达140mAhg-1，并且在循环过程中比容量有所上升，经过100次循环后，其比容量仍可达168.6mAhg-1。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (4)
1.一种多孔无定形TiO2基钠离子电池的制备方法，其特征在于：
具体制备步骤为：
（1）首先将1-4g硫酸氧钛与20-25ml乙醇混合搅拌后倒入装有40-45ml浓度为10-15 M的NaOH反应釜中，最后加入1-2g的NaHCO3，进行水热反应，得到产物再经离心洗涤样品，收集得到白色的多孔无定形TiO2；
（2）钠离子电池组装：将无定形TiO2与乙炔黑、阿拉伯树胶混合研磨，均匀涂在1.2cm2的铜片上做工作电极，采用金属钠片做对电极，电解质是1M NaClO4的EC+DEC溶液；电池组装在氩气保护下手套箱里进行；
步骤（1）中水热反应为具体为150-180℃下反应1-3天。
2.根据权利要求1所述的一种多孔无定形TiO2基钠离子电池的制备方法，其特征在于：步骤（2）中EC与DEC的体积比为1:1。
3.根据权利要求1所述的一种多孔无定形TiO2基钠离子电池的制备方法，其特征在于：步骤（2）中无定形TiO2、乙炔黑、阿拉伯树胶的质量比为75-80：10-15：5-10。
4.一种如权利要求1所述方法制备的多孔无定形TiO2基钠离子电池。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710877801.XA CN107681148B (zh) | 2017-09-26 | 2017-09-26 | 一种多孔无定形二氧化钛基钠离子电池及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710877801.XA CN107681148B (zh) | 2017-09-26 | 2017-09-26 | 一种多孔无定形二氧化钛基钠离子电池及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107681148A CN107681148A (zh) | 2018-02-09 |
| CN107681148B true CN107681148B (zh) | 2020-10-23 |
Family
ID=61138172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710877801.XA Active CN107681148B (zh) | 2017-09-26 | 2017-09-26 | 一种多孔无定形二氧化钛基钠离子电池及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107681148B (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110459407B (zh) * | 2018-05-07 | 2021-05-14 | 福建师范大学 | 层状多孔纳米片二氧化钛基钠离子混合电容器的制备方法 |
| CN108987712B (zh) * | 2018-07-20 | 2021-10-01 | 福建师范大学 | 一种钠离子电池负极材料的制备方法 |
| CN109360979B (zh) * | 2018-10-17 | 2021-07-27 | 福建师范大学 | 一种磷酸根修饰的多孔二氧化钛及其在钠离子电池中的应用 |
| CN111600008A (zh) * | 2020-04-23 | 2020-08-28 | 江苏师范大学 | 一种二氧化钛钠离子电池负极材料制备方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1422198A1 (en) * | 2001-07-27 | 2004-05-26 | Chiyoda Corporation | Porous 4 group metal oxide and method for preparation thereof |
| CN104617284A (zh) * | 2015-02-05 | 2015-05-13 | 福建师范大学 | 一种多孔四方片状TiO2及其制备方法和应用 |
| CN106252624A (zh) * | 2016-08-26 | 2016-12-21 | 先进储能材料国家工程研究中心有限责任公司 | 锂电池负极用多孔二氧化钛及其制备方法 |
| CN106935855A (zh) * | 2017-03-24 | 2017-07-07 | 中南大学 | 一种多孔碳纳米管状材料及其制备方法和应用 |
-
2017
- 2017-09-26 CN CN201710877801.XA patent/CN107681148B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1422198A1 (en) * | 2001-07-27 | 2004-05-26 | Chiyoda Corporation | Porous 4 group metal oxide and method for preparation thereof |
| CN1533363A (zh) * | 2001-07-27 | 2004-09-29 | ǧ���ﻯ��������ʽ���� | 多孔4族金属氧化物及其制备方法 |
| CN104617284A (zh) * | 2015-02-05 | 2015-05-13 | 福建师范大学 | 一种多孔四方片状TiO2及其制备方法和应用 |
| CN106252624A (zh) * | 2016-08-26 | 2016-12-21 | 先进储能材料国家工程研究中心有限责任公司 | 锂电池负极用多孔二氧化钛及其制备方法 |
| CN106935855A (zh) * | 2017-03-24 | 2017-07-07 | 中南大学 | 一种多孔碳纳米管状材料及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107681148A (zh) | 2018-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107681148B (zh) | 一种多孔无定形二氧化钛基钠离子电池及其制备方法 | |
| CN108899486B (zh) | 包覆硫系电解质的正极活性材料及其制备方法、全固态锂硫电池及其制备方法 | |
| CN104617271B (zh) | 一种用于钠离子电池的硒化锡/氧化石墨烯负极复合材料及其制备方法 | |
| CN106450265B (zh) | 一种原位氮掺杂碳包覆钛酸锂复合电极材料及其制备方法 | |
| CN104124431B (zh) | 一种锂离子电池用石墨负极材料及其制备方法 | |
| Li et al. | Pencil-drawing on nitrogen and sulfur co-doped carbon paper: An effective and stable host to pre-store Li for high-performance lithium–air batteries | |
| CN103500826B (zh) | 一种石墨烯—锂电池正极复合材料的制备方法 | |
| CN104538207B (zh) | TiNb2O7/碳纳米管复合材料的制备方法及以该材料为负极的锂离子电容器 | |
| CN105140477A (zh) | 硅碳复合材料及其制备方法 | |
| CN111517374B (zh) | 一种Fe7S8/C复合材料的制备方法 | |
| CN106229498A (zh) | 一种适用于水系金属离子电池的负极材料及其制备方法 | |
| CN104795543B (zh) | 一种凹凸棒基硫复合材料及其制备方法和储能应用 | |
| CN105514378A (zh) | 一种仿细胞结构锂硫电池正极复合材料及其制备方法 | |
| CN106058151B (zh) | 碳纳米管/纳米硫/聚苯胺复合电极、制备方法及应用 | |
| CN109755554A (zh) | 一种铝硒二次电池 | |
| CN109037552A (zh) | 一种用于钠硫电池的隔膜材料的制备方法 | |
| CN106853968A (zh) | 一种多元素共掺杂铅炭电池用活性炭的制备方法 | |
| CN108172406A (zh) | 一种以FeS2-xSex材料为负极材料的钠离子电容器 | |
| Peng et al. | Synergistic effects of an artificial carbon coating layer and Cu2+-electrolyte additive for high-performance zinc-based hybrid supercapacitors | |
| CN103972466A (zh) | 一种高温锂亚硫酰氯电池的正极及其制备方法 | |
| CN108615854A (zh) | 一种硅基锂离子电池负极活性材料及其制备和应用 | |
| CN103746094A (zh) | C-LiFePO4/PTPAn复合材料、其应用以及由其制备的锂电池 | |
| CN106229501B (zh) | 一种纳米带状镁锰氧化物及水系镁离子电池电极的制备方法 | |
| Pan et al. | N-doped carbon coated NaV3O8 cathodes towards high-capacity and ultrafast Na-ion storage | |
| Yu et al. | Modifying the Zn Anode with Nano-Silica: A Strategy to Realize Dendrite-Free Zinc-Ion Hybrid Supercapacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240122 Address after: 518000, Unit A604-09, Innovation Plaza, 2007 Pingshan Avenue, Liulian Community, Pingshan Street, Pingshan District, Shenzhen, Guangdong Province Patentee after: Zhongna Era (Shenzhen) New Energy Technology Co.,Ltd. Country or region after: China Address before: Room 303, Building 2, No. 16 Keji Fourth Road, Songshan Lake Park, Dongguan City, Guangdong Province, 523000 Patentee before: Zhisheng Information Technology (Dongguan) Co.,Ltd. Country or region before: China Effective date of registration: 20240122 Address after: Room 303, Building 2, No. 16 Keji Fourth Road, Songshan Lake Park, Dongguan City, Guangdong Province, 523000 Patentee after: Zhisheng Information Technology (Dongguan) Co.,Ltd. Country or region after: China Address before: Fujian Normal University Qishan Campus, No.1 Science and Technology Road, University City, Shangjie Town, Minhou County, Fuzhou City, Fujian Province, 350117 Patentee before: Fujian Normal University Country or region before: China |
|
| TR01 | Transfer of patent right |