WO2006032183A1 - A METHOD OF MANUFACTURING A LAYERED CoAl DOUBLE HYDROXIDE COMPOSITE METAL OXIDES ELECTRODE MATERIALS - Google Patents

A METHOD OF MANUFACTURING A LAYERED CoAl DOUBLE HYDROXIDE COMPOSITE METAL OXIDES ELECTRODE MATERIALS Download PDF

Info

Publication number
WO2006032183A1
WO2006032183A1 PCT/CN2005/001227 CN2005001227W WO2006032183A1 WO 2006032183 A1 WO2006032183 A1 WO 2006032183A1 CN 2005001227 W CN2005001227 W CN 2005001227W WO 2006032183 A1 WO2006032183 A1 WO 2006032183A1
Authority
WO
WIPO (PCT)
Prior art keywords
cobalt
solution
carbonate
aluminum
composite metal
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.)
Ceased
Application number
PCT/CN2005/001227
Other languages
English (en)
French (fr)
Inventor
Xue Duan
Wensheng Yang
Yi Wang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Publication of WO2006032183A1 publication Critical patent/WO2006032183A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention relates to a preparation method of a layered structure cobalt-aluminum bishydroxy composite metal oxide supercapacitor electrode material, belonging to the technical field of supercapacitor electrode material preparation. Background technique
  • Supercapacitors combine the advantages of high energy density of secondary batteries and high power density of conventional physical (or electrolytic) capacitors. They are also environmentally friendly, have a wide operating temperature range, and have long cycle life. They are extremely promising. New energy storage devices have broad application prospects in electric vehicles, mobile communications, aerospace, defense technology and new energy development. Electrode materials are an important part of supercapacitors and are the key factors affecting the performance and production cost of supercapacitors. Therefore, research and development of high-performance, low-cost electrode materials is an important part of supercapacitor research and development.
  • the activated carbon material has stable performance and low price. It has been commercialized in Japan, the United States, Russia and China. However, the internal resistance of the carbon material electrode is large, and it is not suitable for working under high current. In addition, the specific capacitance is low, and the single electrode mass ratio is generally At 100-300 Fg- 1 (the mass does not include diaphragm, electrolyte and collector quality).
  • the noble metal oxide has a higher specific capacitance (the nanocrystalline yttrium oxide single electrode mass ratio capacitance is 380 Fg" 1 , the amorphous hydrated yttrium oxide is up to 760 Fg" 1 ), and the electrical conductivity is large (larger than the carbon material) It is the most excellent supercapacitor electrode material, and it has been applied to aerospace, military and other important fields. However, 4 resources are limited, expensive, and cannot be universally applied. Therefore, the search for electrode materials with abundant resources, low cost and excellent performance has become the focus of research in supercapacitors. Studies have shown that manganese oxide, cobalt oxide, nickel oxide and the like have electrochemical properties similar to those of cerium oxide, and are expected to become Alternative materials for cerium oxide based supercapacitors.
  • Liu Xianming et al. considered the use of doping A1 to improve the electrochemical performance of electroactive materials, and prepared a layered structure of cobalt aluminum by chemical coprecipitation. Double hydroxide Co. . 67 Al. . 33 (C0 3 ). 165 (0H) 2 ⁇ nH 2 0, the single-electrode mass ratio capacitance reaches 400 Fg" 1 , but the crystal form of the sample prepared by this method is not good enough, and the agglomeration phenomenon between the particles is serious.
  • An object of the present invention is to provide a method for preparing a layered structure cobalt aluminum bishydroxy composite metal oxide (Co-Al-LDHs) supercapacitor electrode material.
  • the invention utilizes the full back mixed liquid membrane reactor device described in Chinese Patent ZL00132145. 5 to prepare a cobalt-aluminum bishydroxy composite metal oxide layered material having a nanometer size, uniform particle size and good properties, and then is baked at a certain temperature.
  • the electrochemical active sites of cobalt are sufficiently exposed on the _S ⁇ of the cobalt-aluminum bishydroxy composite metal oxide layered structure, thereby obtaining nanometer-level uniform dispersion, high specific capacitance, good rate characteristics, and good electrochemical cycle performance.
  • Layered structure cobalt aluminum bishydroxy composite metal oxide supercapacitor electrode material.
  • the mixed salt solution has a metal ion concentration of 0. 5-2.
  • the mixed salt solution is mixed with a salt solution A.
  • the mixed metal salt concentration is 0. 5-2 0 mo l -L" 1 ;
  • B. Add the soluble carbonate or acid carbonate and sodium hydroxide or ammonia water to the deionized water to prepare the alkaline solution B, so that the alkali solution B and the solution A are the same volume, wherein the amount of sodium hydroxide or ammonia water and the solution A 5-3: 1 ;
  • the molar ratio of the amount of the carbonate or the acid carbonate is 0. 5-3: 1 ;
  • the mixed salt solution A and the alkali solution B are simultaneously added to the full back-mixed membrane reactor at the same speed, and the liquid distributor is thoroughly mixed at the gap between the rotor and the stator, and discharged through the discharge port, and controlled.
  • the rotor speed is 1000-6000 rmp
  • the reaction temperature is 15-35 °C
  • the residence time of the material in the reactor is 1-5 min, and then placed in the crystallization tank, crystallized under stirring, crystallization temperature Control at 30-90 °C, crystallization time 5-20 h.
  • the precipitate after crystallization is filtered off, washed several times with deionized water to a pH of less than 8, and then dried under vacuum at 60-80 °C for 5-10 h.
  • step D The material dried in step D is heated to 140-200 ° C at a rate of 1-5 ° C.min -1 , thermostatically for 2 - 10 h, and then cooled to room temperature with a furnace to obtain the product of the invention.
  • the soluble divalent cobalt salt described in the step A is cobalt nitrate Co(N0 3 ) 2 , cobalt chloride (0 (1 2 or cobalt sulfate CoS0 4 ⁇ , and the soluble aluminum salt is aluminum nitrate A1 (N0 3 )). 3. Any one of aluminum chloride A1C1 3 or aluminum sulfate A1 2 (S0 4 ) 3 .
  • the soluble carbonate or acid carbonate described in Step B is sodium carbonate Na 2 C0 3 , sodium hydrogencarbonate NaHC0 3 ⁇ potassium carbonate K 2 C0 3 , potassium hydrogencarbonate KHC0 3 , ammonium carbonate ( 4 ) 2 C0 3 Any of ammonium hydrogencarbonate NH 4 HC0 3 . : ''
  • the structural feature of the full back mixed liquid membrane reactor used in step C is that a closed casing is used as a stator, and a stator has a rotatable cone-shaped rotor.
  • the taper of the rotor is 50 - 70 degrees, and the inner cavity of the stator is
  • the rotor has the same taper shape, the outer surface of the rotor and the inner surface of the stator respectively have grooves, and the groove on the inner surface of the stator has a spiral shape, and the groove on the outer surface of the rotor has the same shape and number of grooves as the stator.
  • the ratio of the groove width to the groove depth of the groove is 1-5:1, and the ratio of the number of grooves on the rotor to the number of centimeters of the largest diameter of the rotor is 2-3:1;
  • the end of the cross-sectional area is provided with a liquid distributor, the stator is provided with a raw material feed port and a discharge port, and the feed port is located at a small cross-sectional area of the rotor At one end, the discharge port is located at one end of the rotor having a large cross-sectional area, and a gap of adjustable size is left between the inner surface of the stator and the outer surface of the rotor.
  • the content of cobalt and aluminum in the product was determined by inductively coupled plasma emission spectroscopy (ICP) of Shimadzu ICPS-7500.
  • the electrode material Co-Ai-LDHs prepared by the present invention is mixed with a commercially available acetylene black conductive agent and a polytetrafluoroacetic acid binder at a mass fraction of 70:20:10, compressed to a thickness of 100 ⁇ m, and transferred to
  • the foamed nickel current collector is used as the working electrode
  • the Hg/HgO electrode is the reference electrode
  • the large area platinum wire is the auxiliary electrode
  • the 6 mol.L- 1 K0H aqueous solution is assembled into a three-electrode test system. Cyclic voltammetry was performed using the IM6e electrochemical workstation of ZAHNER, Germany. The potential sweep range was -0. 15-0. 60 V (vs.
  • the battery tester performs a constant current charge and discharge test, and the charge and discharge voltage ranges from -0. 15-0. 5 V (vs. Hg/HgO), and the current density is 60-500.
  • the mass specific capacitance of the product of the invention is above 600 Fg -1 , which is higher than reported in the literature, and has good rate characteristics and electrochemical cycle performance.
  • the remarkable effects of the present invention are as follows: "The method of the present invention can be used to prepare a layered structure cobalt aluminum bishydroxy composite metal oxide having nanometer size, uniform particle size, good dispersibility and sufficient electrochemical exposure of cobalt.
  • Supercapacitor electrode material, and this material has the advantages of higher capacitance, better rate characteristics, and better electrochemical cycle performance.
  • Figure 4 is a graph of charge and discharge curves of Co-Al-LDHs calcined at 160 °C at different current densities.
  • the gap between the gaps is fully mixed, discharged from the discharge port, the rotor speed is controlled to 4000 rpm, the reaction temperature is 25 °C, the residence time of the material in the reactor is 2 min; the slurry discharged from the full back-mixed membrane reactor is rounded In the bottom flask, the crystal was stirred for 10 h in a water bath at 80 ° C; the crystallized material was washed several times with deionized water, filtered to a H value of less than 8, and then vacuum dried at 80 ° C for 5 h; The dried material was heated at a rate of 2 ° C - min -1 to a constant temperature of 160 ° C for 5 h, and then cooled to room temperature with a furnace to obtain the product of the present invention.
  • the ICP test showed that the molar ratio of Co/Al in the product was 2:1; XRD test showed that the product had a good crystal form, belonging to the hexagonal system, and the layered structure of LDHs was obvious (see Fig. 1); HRTEM test showed the product grain The diameter is in the range of 30-50 run, and the dispersion is good (see Figure 2).
  • Electrochemical cyclic voltammetry The test shows that the oxidation process of the cyclic voltammetry curve of the product is symmetric with the reduction process, and the electrode potential is 100mV-400mV (vs The range of Hg/Hg0) is close to square, indicating that the supercapacitor characteristics are obvious (see Figure 3); the charge-discharge test at 60-480 mA.g- 1 current density indicates that the product mass-to-capacitance is above 680 Fg" 1 , product The rate characteristics are good (see Figure 4), and the capacity is not significantly attenuated after 100 weeks of charge and discharge.
  • the slurry discharged from the full back-mixed membrane reactor is placed in a round bottom flask at 65 °.
  • C is crystallization for 15 h in a water bath; the crystallized material is washed several times with deionized water, filtered to a pH of less than 8, and then dried under vacuum at 70 ° C for 5 h; the dried material is 2 O
  • the rate of .min- 1 was raised to 200 ° C for 5 h, and then cooled to room temperature with the furnace to obtain the product of the present invention.
  • the ICP test showed that the molar ratio of Co/Al in the product was 4:1; XRD test showed that the product had a good crystal form, belonging to the hexagonal system, and the layered structure of LDHs was obvious; HRTEM test showed that the product particle size was 30-50 nm The range and dispersion are good; the mass ratio capacitance at 100 mA.g- 1 current density is above 610, and the capacity is not significantly attenuated after 100 weeks of charge and discharge.
  • test product molar ratio Co / Al of 3: 1 XRD tests showed that the product has a good crystal form, a hexagonal system, lamellar structure LDHs obvious characteristics; tests show the HRTEM product particle size 30-50 The range of nm is good and the dispersion is good.
  • the mass-to-capacitance at 80 mA.g current density is above 650 Fg- 1 , and the capacity is not significantly attenuated after 100 weeks of charge and discharge.

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Description

一种层状钴铝双羟基复合金属氧化物电极材料的制备方法 技术领域
本发明涉及一种层状结构鈷铝双羟基复合金属氧化物超级电容器电极 材料的制备方法， 属超级电容器电极材料制备技术领域。 背景技术
超级电容器兼有二次电池能量密度高及常规物理（或电解）电容器功率 密度大的优点， 此外还具有对环境友好、 工作温度范围宽、 循环寿命长等特 点， 是一种极有发展前景的新型储能器件，在电动车、移动通讯、航空航天、 国防科技和新能源开发等方面具有广阔应用前景。 电极材料是超级电容器的 重要组成部分， 是影响超级电容器性能和生产成本的关键因素， 因此研究开 发高性能、 低成本电极材料是超级电容器研究开发工作的重要内容。
活性炭材料性能稳定， 价格便宜， 在日本、 美国、 俄罗斯及中国均已产 品化， 但炭材料电极内阻较大， 不适宜在大电流下工作， 另外比电容偏低， 单电极质量比电容一般在 100- 300 F.g— 1 (该质量不包括隔膜、 电解质及集流 体质量） 。
, 贵金属氧化物（氧化钌）具有比电容高 （纳米晶氧化钌单电极质量比电 容为 380 F.g"1 , 无定形水合氧化钌高达 760 F.g"1 ) 、 电导率大（比炭材料大 两个数量级）及在电解液中稳定等优点， 是目前性能最为优良的超级电容器 电极材料， 美国已将其应用于航空航天、 军事等重要领域。 但 4了资源有限、 价格昂贵， 无法普及应用。 因此寻找资源丰富、 价^ ί氏廉、 性能优良的电极 材料成为超级电容器研究领域的焦点， 已有研究表明， 氧化锰、 氧化钴、 氧 化镍等具有与氧化钌类似的电化学性能， 有望成为氧化钌基超级电容器的替 代材料。
在文献（1) : Journal of the Electrochemical Society, 1998， 145 (12)， p4097 中， Chuan Lin等人采用溶胶 -凝胶方法制备了 Co (0H) 2干凝胶， 在 150 °C焙烧处理得到的 Co0x的最高单电极比电容为 291 F.g-'。 但此制备方法 复杂， 并且产物的比电容偏低， 活性物质并未得到充分利用。
在文献（2) : 电源技术， 2003, 27 (3)， p315中， 刘献明等人考虑到利用 掺杂 A1提高电活性物质的电化学性能， 采用化学共沉淀方法制备了层状结 构的钴铝双氢氧化物 Co。.67Al。.33 (C03)。.165 (0H) 2 · nH20, 单电极质量比电容达到 400 F-g"1, 但此方法制备出的样品的晶型不够好， 并且颗粒间的团聚现象严 重。
为了提高钴铝双氢氧化物的晶化程度， 在文献（3) : 应用化学， 2003, 20 (6) , p524 中， 刘献明等人将文献（2)中合成出的样品在 130 °C水热处理 16 h, XRD谱图表明水热处理后的样品的晶型明显变好， 但水热处理后单电 极比电容仅提高 15%， 达到 460 F.g一1。 发明内容
本发明的目的是提供一种层状结构钴铝双羟基复合金属氧化物 (Co-Al-LDHs) 超级电容器电极材料的制备方法。
本发明利用中国专利 ZL00132145. 5 中记载的全返混液膜反应器装置， 制备纳米尺寸、粒径均一、 性好的钴铝双羟基复合金属氧化物层状材料， 然后在一定温度下进行焙烧， 在保持钴铝双羟基复合金属氧化物层状结构的 _S ^出上使钴的电化学活性位充分暴露，从而获得纳米级均匀分散、比电容高、 倍率特性好、 电化学循环性能佳的层状结构钴铝双羟基复合金属氧 物超级 电容器电极材料。
本发明的具体步骤如下：
A. 将可溶性二价钴盐和可溶性铝盐按 Co/Al摩尔比为 1-5: 1的比例 溶于去离子水中配制混合盐溶液 A， 混合盐溶液中金属离子浓度为 0. 5-2. 0 mo l -L"1; B. 将可溶性碳酸盐或酸式碳酸盐与氢氧化钠或氨水加入去离子水中配 制碱性溶液 B， 使碱溶液 B与溶液 A体积相同， 其中氢氧化钠或氨水的量与 溶液 A中钴盐的摩尔比为 1-4: 1，碳酸盐或酸式碳酸盐的量与溶液 A中铝盐 的摩尔比为 0. 5-3： 1 ;
C. 分别将混合盐溶液 A与碱溶液 B同时等速加入到全返混液膜反应器 中， 经液体分布器^^在转子与定子之间的缝隙处充分混合， 经出料口排 出， 控制转子转速为 1000- 6000 rmp, 反应温度为 15- 35 °C , 物料在反应器 内的停留时间为 1-5 min, 然后放入晶化釜内， 在搅拌状态下进行晶化， 晶 化温度控制在 30-90 °C， 晶化时间 5-20 h。
D. 将晶化后的沉淀物滤出， 用去离子水多次洗涤至 pH值小于 8， 然后 在 60- 80 °C真空干燥 5-10 h。
E. 将步骤 D干燥后的物质以 1-5 °C .min— 1的速率升温至 140- 200 °C， 恒温 2- 10 h, 然后随炉冷却至室温， 获得本发明产品。
步骤 A所述的可溶性二价钴盐为硝酸钴 Co (N03) 2、氯化钴（0( 12或硫酸钴 CoS04†的任意一种， 可溶性铝盐为硝酸铝 A1 (N03) 3、 氯化铝 A1C13或硫酸铝 A12 (S04) 3中的任意一种。
步骤 B 所述的可溶性碳酸盐或酸式碳酸盐是碳酸钠 Na2C03、 碳酸氢钠 NaHC03^ 碳酸钾 K2C03、 碳酸氢钾 KHC03、 碳酸铵 ( 4) 2C03、 碳酸氢铵 NH4HC03 中任何一种。 ： ' '
步骤 C采用的全返混液膜反应器的结构特点是， 由一封闭的机壳作为定 子， 定子内有一可旋转的锥体状转子， 转子的锥度为 50 - 70度， 定子的内腔 为与转子锥度相同的锥体状， 转子的外表面和定子的内表面分别带有凹槽， 定子内表面的凹槽呈螺旋状， 转子外表面的凹槽与定子的凹槽形状、 个数相 同， 但呈相反方向的螺旋状， 凹槽的槽宽与槽深比为 1-5: 1 , 转子上凹槽的 个数与转子的最大直径的厘米数之比为 2-3: 1; 转子横截面积小的一端带有 液体分布器， 定子上设有原料进料口和出料口， 进料口位于转子横截面积小 的一端， 出料口位于转子横截面积大的一端， 定子内表面与转子外表面之间 留有一个可以调节大小的缝隙。
采用日本岛津 ICPS- 7500型电感耦合等离子体发射光语仪（ICP)测定产 物中钴和铝的含量， 根据钴盐和铝盐投料量的不同， 产物中 Co/Al的摩尔比 为 2- 4: 1; 曰本岛津 XRD- 6000型 X射线粉末衍射仪（XRD ) ( Cu Ka辐射， λ = 1. 5406 )表征产物结构， 属于六方晶系， 具有层状结构， Co- A1- LDHs 的 003、 006和 009三个特征峰高而尖锐（请参阅图 1所示） ， 表明产物具 有较高的结晶度； 日本电子 JEM- 2010高分辨透射电镜（HRTEM)观察样品的表 面形貌和粒径， 产物粒径为 30-60 nm, 并且粒径均一， 分散性好。
将本发明制备的电极材料 Co-Ai- LDHs与市售乙炔黑导电剂和聚四氟乙 浠粘结剂按 70: 20: 10的质量分数混合， 压片至 100 μιη的厚度， 转压到发 泡镍集流体上作为工作电极， Hg/HgO 电极为参比电极， 大面积铂丝为辅助 电极， 6 mol.L— 1的 K0H 水溶液为电解液组装成三电极测试体系。 利用德国 ZAHNER 公司 IM6e 电化学工作站进行循环伏安测试， 电位扫描范围为 -0. 15-0. 60 V (vs. Hg/HgO) , 扫描速率 ImV.s— '； 采用武汉蓝电 BTI1- 10型电池 测试仪进行恒电流充放电测试，充放电电压范围为 -0. 15-0. 5 V (vs. Hg/HgO) , 电流密度为 60- 500 . 。 本发明产品的质量比电容均在 600 F.g—1以上， 高 于文献报道值， 并且具有良好的倍率特性及电化学循环性能。
本发明的显著效果是: "采用本发明提供的方法可以制备出具有纳米尺 寸、 粒径均一、 分散性好且鈷的电化学活性位能够充分暴露的层状结构钴铝 双羟基复合金属氧化物超级电容器电极材料， 并且该材料具有比电容高、 倍 率特性好、 电化学循环性能佳的优点。 附图说明 ·
图 1为 Co/Al=2的 Co-Al- LDHs的 X-射线衍射谱图。
图 2为 Co/Al=2的 Co - Al-LDHs的高分辨透射电镜及选区电子衍射照片。 图 3为 160 °C焙烧 Co/Al=2的 Co- Al-LDHs的循环伏安曲线图。
图 4为 160 °C焙烧 Co/Al=2的 Co- Al-LDHs在不同电流密度下的充放电 曲线图。 具体实施方式 实施例 1
取 0. 10 mol的 Co (N03) 2^ 0. 05 mol的 A1 (N03) 3溶于 150 ml的去离子水 中配成混合盐溶液， 取 0. 20 mol的 aOH和 0. 10 mol的 Na2C03溶于 150 ml 的去离子水中配成碱溶液； 将混合盐溶液与碱溶液分别同时等速加入到全返 混液膜反应器中， 经液体分布器分散后在转子与定子之间的缝隙处充分混 合， 由出料口排出， 控制转子转速为 4000rmp, 反应温度为 25 °C , 物料在反 应器内的停留时间为 2 min; 将全返混液膜反应器排出的浆液^ 圆底烧瓶 中，在 80 °C的水浴下搅拌晶化 10 h; 将晶化后的物质用去离子水多次洗涤、 过滤，至 H值小于 8，然后在 80°C真空干燥 5 h;将干燥后的物质以 2 °C -min-1 的速率升温至 160 °C恒温焙烧 5 h， 然后随炉冷却至室温，获得本发明产品。 ICP测试表明产物中 Co/Al的摩尔比例为 2: 1; XRD测试表明产物具有良好 的晶型， 属六方晶系， LDHs的层状结构特征明显（见图 .1 ) ； HRTEM测试表 明产物粒径在 30-50 run范围， 且分散性 好（见图 2 )； 电化学循环伏安测： 试表明产物的循环伏安曲线的氧化过程与还原过程对称， 且在电极电势 100mV-400mV (vs. Hg/Hg0)范围内接近方形，表明超电容特性明显（见图 3 ); 60-480 mA.g— 1电流密度下的充放电测试表明产物质量比电容均在 680 F-g"1 以上， 产物倍率特性好（见图 4 ) , 充放电 100周后容量无明显衰减。 实施例 2
取 0. 20 mol的 CoS04和 0. 025 mol的 A12 (S04) 3溶于 150 ml的去离子水 中配成混合盐溶液， 取 0· 20 mol的 NaOH和 0. 10 mol的 Na2C03溶于 150 ml 的去离子水中配成碱溶液； 将混合盐溶液与碱溶液分别同时等速加入到全返 混液膜反应器中， 经液体分布器分散后在转子与定子之间的缝隙处充分混 合， 由出料口排出， 控制转子转速为 3500 rmp, 反应温度为 35 °C , 物料在 反应器内的停留时间为 1 min; 将全返混液膜反应器排出的浆液放入圓底烧 瓶中， 在 65 °C的水浴下搅拌晶化 15 h; 将晶化后的物质用去离子水多次洗 涤、 过滤， 至 pH值小于 8， 然后在 70 °C真空干燥 5 h; 将干燥后的物质以 2 O.min— 1的速率升温至 200 °C恒温焙烧 5 h, 然后随炉冷却至室温， 获得本 发明产品。 ICP测试表明产物中 Co/Al的摩尔比为 4: 1 ; XRD测试表明产物 具有良好的晶型， 属六方晶系， LDHs的层状结构特征明显； HRTEM测试表明 产物粒径在 30- 50 nm范围， 且分散性良好； 100 mA.g—1电流密度下的质量比 电容在 610 以上， 充放电 100周后容量无明显衰减。 实施例 3
取 0. 15 mol的 CoCl2和 0. 05 mol的 A1C13溶于 150 ml的去离子水中配 成混合盐溶液， 取 0. 15 mol的 NaOH和 0, 10 mol的 Na2C03溶于 150 ml的去 离子水中配成碱溶液； 将混合盐溶液与碱溶液分别同时等速加入到全返混液 膜反应器中， 经液体分布器分散后在转子与定子之间的缝隙处充分混合， 由 出料口 出， 控制转子转速为 5000 rmp, 反应温度为 25 °C , 物料在反应器 内的停留时间为 3 min; 将全返^液膜反应器排出的浆 圆底烧瓶中， 在 70 °C的水浴下搅拌晶化 15 h; 将晶化后的物质用去离子水多次洗涤、 过 滤，至 pH值小于 8 ,然后在 80 °0真空干燥 10 h;将干燥后的物质以 5 °C .min-' 的速率升温至 160 °C恒温焙烧 5 h， 然后随炉冷却至室温，获得本发明产品。 ICP测试表明产物中 Co/Al的摩尔比例为 3: 1; XRD测试表明产物具有良好 的晶型， 属六方晶系， LDHs的层状结构特征明显； HRTEM测试表明产物粒径 在 30- 50 nm 范围， 且分散性良好； 80 mA.g 电流密度下的质量比电容在 650 F.g— 1以上， 充放电 100周后容量无明显衰减。

Claims

权利要求书
1. 一种层状钴铝双羟基复合金属氧化物电极材料的制备方法， 具体步 骤如下：
A. 将可溶性二价钴盐和可溶性铝盐按 Co/Al的摩尔比为 1-5 : 1的比 例溶于去离子水中配制混合盐溶液 A , 该混合盐溶液中金属离手浓度为
0. 5-2. 0 mol .L—
B. 将可溶性碳酸盐或酸式碳酸盐与氢氧化钠或氨水加入去离子水中配 制碱性溶液 B, 使溶液 B与溶液 A体积基本相同， 其中氢氧化钠或氨水的量 与溶液 A中钴盐的摩尔比为 1-4: 1 ,碳酸盐或酸式碳酸盐的量与溶液 A中铝 盐的摩尔比为 0. 5-3: 1 ;
C.分别将混合盐溶液 A与碱溶液 B 同时等速加入到全返混液膜反应器 中， 经液体分布器分散后在转子与定子之间的缝隙处充分混合， 经出料口排 出， 控制转子转速为 1000-6000 rmp, 反应温度为 15- 35 °C , 物料在反应器 内的停留时间为 1-5 min, 然后放入晶化釜内， 在搅拌状态下进行晶化， 晶 化温度控制在 30- 90 °C， 晶化时间为 5-20 h;
D.将晶化后的沉淀物滤出， 用去离子水洗涤至 pH值小于 8 , 然后在 60- 8 (TC真空干燥 5-10 h;
E.将步骤 D干燥后的物质以 1-5 O .min— 1的速率升温至 140- 200 °C , 恒 ¾ 2-10 h， 然后随炉冷却至室温， 获得本发明产 P 。
2. 权利要求 1所述的层状鈷铝双羟基复合金属氧化物电极材料的制备 方法， 其特征是：
步骤 A所述的可溶性二价钴盐为硝酸钴 Co (N03) 2、氯化钴（0(：12或硫酸钴 CoS04中的任意一种； 可溶性铝盐为硝酸铝 A1 (N03) 3、 氯化铝 A1C13或石克酸铝 A12 (S04) 3中的任意一种；
步骤 B 所述的可溶性碳酸盐是碳酸钠 Na2C03、 碳酸钾 K2C03、 碳酸铵
(NH4) 2C03, 可溶性酸式碳酸盐是碳酸氢钠 NaHC03、碳酸氢钾 MC03、碳酸氢铵 NH4HC03中任何一种。
PCT/CN2005/001227 2004-09-21 2005-08-10 A METHOD OF MANUFACTURING A LAYERED CoAl DOUBLE HYDROXIDE COMPOSITE METAL OXIDES ELECTRODE MATERIALS Ceased WO2006032183A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200410077946.4 2004-09-21
CNB2004100779464A CN100485836C (zh) 2004-09-21 2004-09-21 一种层状钴铝双羟基复合金属氧化物电极材料的制备方法

Publications (1)

Publication Number Publication Date
WO2006032183A1 true WO2006032183A1 (en) 2006-03-30

Family

ID=36089836

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2005/001227 Ceased WO2006032183A1 (en) 2004-09-21 2005-08-10 A METHOD OF MANUFACTURING A LAYERED CoAl DOUBLE HYDROXIDE COMPOSITE METAL OXIDES ELECTRODE MATERIALS

Country Status (2)

Country Link
CN (1) CN100485836C (zh)
WO (1) WO2006032183A1 (zh)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110404501A (zh) * 2019-08-08 2019-11-05 宝鸡文理学院 一种核-壳结构层状双金属氢氧化物复合粒子的制备方法
CN110921721A (zh) * 2019-12-03 2020-03-27 西北师范大学 一种基于金属有机框架衍生的双金属氢氧化物的制备及应用
CN111508718A (zh) * 2020-04-01 2020-08-07 安徽师范大学 一种Co2Al/Co2Mn电极复合材料及其制备方法
CN113307312A (zh) * 2021-05-27 2021-08-27 辽宁工程技术大学 一种碱硫复合处理钴铬镍水滑石超级电容电极材料的方法
CN114420460A (zh) * 2021-12-22 2022-04-29 宁波诺丁汉新材料研究院有限公司 一种全磷酸盐电极材料及其制备方法
CN114573011A (zh) * 2022-03-18 2022-06-03 北京化工大学 一种可控制备不同厚度超薄复合金属氢氧化物的方法
CN114933294A (zh) * 2022-05-13 2022-08-23 西安交通大学 一种高体积密度多层致密多孔碳纳米片及制备方法和应用
CN115140779A (zh) * 2022-05-05 2022-10-04 中南大学 一种六边形氯插层钴铝类水滑石除氟材料及其制备和应用
CN118908294A (zh) * 2024-07-10 2024-11-08 合肥工业大学 一种磷掺杂钴铝/碳基复合材料制备方法及材料和应用
CN120864542A (zh) * 2025-09-24 2025-10-31 山东保蓝环保有限公司 固废煤矸石原位晶化合成铝基水滑石及其制备方法和应用

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1917108B (zh) * 2006-08-02 2010-09-08 北京化工大学 钴铝双羟基复合金属氧化物纳米片薄膜电极及其制备方法
CN100430132C (zh) * 2006-09-27 2008-11-05 北京化工大学 一种用于醇氧化反应合成水滑石薄膜催化剂的制备方法
CN101665233B (zh) * 2009-09-15 2012-06-06 北京化工大学 一种层状双金属氢氧化物及其制备方法
CN101817510A (zh) * 2010-04-17 2010-09-01 湖州师范学院 一种水滑石的制备方法
CN102263261B (zh) * 2011-06-21 2013-04-24 中南大学 一种锌铝水滑石在制备锌镍二次电池锌负极中的应用方法
CN102944908B (zh) * 2012-10-11 2016-03-30 京东方科技集团股份有限公司 一种彩色滤光片、其制备方法和液晶显示装置
CN106057482B (zh) * 2016-06-14 2018-11-02 北京工业大学 一种多级结构LDH@CoS复合电极及制备方法
CN107086312B (zh) * 2017-05-09 2019-08-27 天津大学 合成氧化亚钴与钴铁层状双金属氢氧化物复合物的方法
CN107069013B (zh) * 2017-06-08 2021-01-26 宁波富理电池材料科技有限公司 一种改性富锂锰基正极材料及其制备方法
CN107268021B (zh) * 2017-06-26 2019-08-09 河南大学 一种NiCoAl-LDH修饰三氧化二铁复合光阳极材料及其制备方法和应用
CN109453777A (zh) * 2018-11-26 2019-03-12 中国华能集团清洁能源技术研究院有限公司 基于三元层状双金属氢氧化物提高α-Fe2O3光电催化分解水制氢性能的方法
CN109950482B (zh) * 2019-02-22 2022-06-07 南通金通储能动力新材料有限公司 一种铝掺杂钴酸锂正极材料的制备方法
CN111268708A (zh) * 2020-02-17 2020-06-12 北京化工大学 一种卤素阴离子插层水滑石正极材料及其制备方法以及卤素阴离子电池
CN114388277B (zh) * 2021-12-13 2023-08-04 上海应用技术大学 镀钴石墨/钴铝层状氢氧化物超级电容器电极的制备方法
CN114314617B (zh) * 2021-12-23 2023-06-30 北京化工大学 一种从废旧三元锂离子电池正极材料中回收金属的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1358691A (zh) * 2000-12-14 2002-07-17 北京化工大学 全返混液膜反应器及其在制备超细阴离子层状材料中的应用

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1358691A (zh) * 2000-12-14 2002-07-17 北京化工大学 全返混液膜反应器及其在制备超细阴离子层状材料中的应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LIU X AND ZHANG X.: "Capacitance Property of Co-A1 Double Hydroxide After Hydrothermal Treatment.", CHINESE JOURNAL OF APPLIED CHEMISTRY., vol. 20, no. 6, June 2003 (2003-06-01) *
LIU X AND ZHANG X.: "CoA1 layered double hydroxide as electrode materials of supercapacitor.", CHINESE JOURNAL OF POWER SOURCES., vol. 27, no. 3, June 2003 (2003-06-01) *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110404501A (zh) * 2019-08-08 2019-11-05 宝鸡文理学院 一种核-壳结构层状双金属氢氧化物复合粒子的制备方法
CN110921721A (zh) * 2019-12-03 2020-03-27 西北师范大学 一种基于金属有机框架衍生的双金属氢氧化物的制备及应用
CN111508718A (zh) * 2020-04-01 2020-08-07 安徽师范大学 一种Co2Al/Co2Mn电极复合材料及其制备方法
CN113307312A (zh) * 2021-05-27 2021-08-27 辽宁工程技术大学 一种碱硫复合处理钴铬镍水滑石超级电容电极材料的方法
CN114420460A (zh) * 2021-12-22 2022-04-29 宁波诺丁汉新材料研究院有限公司 一种全磷酸盐电极材料及其制备方法
CN114420460B (zh) * 2021-12-22 2024-03-19 宁波诺丁汉新材料研究院有限公司 一种全磷酸盐电极材料及其制备方法
CN114573011A (zh) * 2022-03-18 2022-06-03 北京化工大学 一种可控制备不同厚度超薄复合金属氢氧化物的方法
CN115140779A (zh) * 2022-05-05 2022-10-04 中南大学 一种六边形氯插层钴铝类水滑石除氟材料及其制备和应用
CN115140779B (zh) * 2022-05-05 2023-09-08 中南大学 一种六边形氯插层钴铝类水滑石除氟材料及其制备和应用
CN114933294A (zh) * 2022-05-13 2022-08-23 西安交通大学 一种高体积密度多层致密多孔碳纳米片及制备方法和应用
CN118908294A (zh) * 2024-07-10 2024-11-08 合肥工业大学 一种磷掺杂钴铝/碳基复合材料制备方法及材料和应用
CN120864542A (zh) * 2025-09-24 2025-10-31 山东保蓝环保有限公司 固废煤矸石原位晶化合成铝基水滑石及其制备方法和应用

Also Published As

Publication number Publication date
CN100485836C (zh) 2009-05-06
CN1753115A (zh) 2006-03-29

Similar Documents

Publication Publication Date Title
WO2006032183A1 (en) A METHOD OF MANUFACTURING A LAYERED CoAl DOUBLE HYDROXIDE COMPOSITE METAL OXIDES ELECTRODE MATERIALS
KR101429531B1 (ko) 코어-쉘 이중층 구조를 갖는 리튬이차전지 양극활물질 및 제조방법 그리고, 그 양극활물질을 포함한 리튬이차전지
JP2020109772A (ja) リチウム二次電池用正極活物質及びこれを含むリチウム二次電池
CN102315429B (zh) 锂离子电池正极材料固相法掺杂铝的制备方法
WO2015039490A1 (zh) 富锂正极材料及其制备方法
CN109244390B (zh) 一种锂离子电池用磷掺杂富锂锰基正极材料及其制备方法
CN111689528A (zh) 一种三元材料前驱体及其制备方法和用途
CN102013481A (zh) 一种球形梯度富锂正极材料的合成方法
KR101440241B1 (ko) 리튬이차전지용 nca계열 양극활물질, 그 양극활물질의 제조방법 및 그 양극활물질을 포함한 리튬이차전지
CN108493458B (zh) 一种高性能海胆状氧化镍/钴酸镍微球锂氧气电池正极催化材料及其制备方法
CN106711434A (zh) 一种类海胆状含钠富锂层状正极材料及其制备方法
CN109390564B (zh) 基于锌离子掺杂的三元金属氧化物、其制备方法与应用
CN101567440A (zh) 锂离子电池孔状LiMn2O4正极材料及其制备方法
CN111370690A (zh) 锂离子电池高镍正极材料、其制备方法及应用
CN111463418A (zh) 一种碳包覆硒化镍超薄纳米片复合材料及其制备方法
CN114678511B (zh) 一种蛋黄双壳结构的纳米复合材料及其制备方法与应用
CN105140494A (zh) 一种Fe3O4/Fe/C纳米复合电池电极材料的仿生合成方法
ZHANG et al. Enhancement of lithium storage capacity and rate performance of Se-modified MnO/Mn3O4 hybrid anode material via pseudocapacitive behavior
CN103474629B (zh) 半中空双连续h2v3o8/石墨烯管中线结构同轴纳米线材料及其制备方法和应用
TWI515949B (zh) 鋰離子電池負極材料的製備方法
CN117809987A (zh) 一种过渡金属高熵氧化物、制备方法及其应用
CN112436136B (zh) 含氧空位的钼酸钴纳米棒及其制备方法和应用
CN115083795B (zh) 一种高性能尖晶石型锰酸锂基半固态流体电极及其制备方法
CN102205989A (zh) 电池正极材料LiMn2O4的制备方法
CN109461920B (zh) 镧铝掺杂的高镍层状氧化物材料及其制备方法和应用

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase