WO2016202173A1 - Method for preparing high-purity lithium titanate negative electrode material and use thereof - Google Patents

Method for preparing high-purity lithium titanate negative electrode material and use thereof Download PDF

Info

Publication number
WO2016202173A1
WO2016202173A1 PCT/CN2016/084173 CN2016084173W WO2016202173A1 WO 2016202173 A1 WO2016202173 A1 WO 2016202173A1 CN 2016084173 W CN2016084173 W CN 2016084173W WO 2016202173 A1 WO2016202173 A1 WO 2016202173A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
lithium titanate
negative electrode
titanium dioxide
electrode material
Prior art date
Application number
PCT/CN2016/084173
Other languages
French (fr)
Chinese (zh)
Inventor
于文倩
赵成龙
李丽
王瑛
易江平
张庆朋
陈建伟
王超武
Original Assignee
山东玉皇新能源科技有限公司
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 山东玉皇新能源科技有限公司 filed Critical 山东玉皇新能源科技有限公司
Publication of WO2016202173A1 publication Critical patent/WO2016202173A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte

Definitions

  • the invention belongs to the field of lithium ion batteries, and in particular relates to a preparation method and application of a high-purity lithium titanate anode material.
  • Lithium titanate has attracted extensive attention as a negative electrode material for lithium ion batteries.
  • Lithium titanate is a spinel-type structure, and its structure can provide three-dimensional channels for the diffusion of lithium ions.
  • lithium titanate The unit cell parameters and volume change are small and are referred to as "zero strain" materials. Extremely low volume changes and sufficient lithium ion channels make lithium titanate extremely excellent cycle performance and high rate charge and discharge performance.
  • the common preparation methods of lithium titanate mainly include solid phase reaction method, sol-gel method and hydrothermal reaction method.
  • the solid phase process is simple, but it is often difficult to ensure uniform mixing, and high-temperature calcination results in high energy consumption.
  • the lithium salt volatilizes at high temperature, resulting in low purity of the product; the sol-gel method has high purity and good particle size control.
  • the use of high-cost titanate as a raw material leads to high cost, mainly used in laboratory research; hydrothermal method products have high purity and low cost, but the use of high temperature and high pressure systems requires high equipment and large investment.
  • the electrochemical method is simple, the energy is clean, and the cost is low, which is an ideal synthetic method.
  • Chinese Patent No. CN103290426A discloses "a preparation method of lithium titanate", which uses titanium dioxide as a cathode, graphite as an anode, molten alkali metal halide as an electrolyte, electrolysis at a high temperature, and anodized to obtain lithium titanate. This method can obtain relatively pure lithium titanate, but the production process requires a high-temperature molten state, and it is difficult to accurately control the titanium-lithium ratio to hinder its industrial application.
  • the present invention provides a preparation method and application of a high-purity lithium titanate negative electrode material which can be mass-produced and has good battery performance.
  • a method for preparing a high-purity lithium titanate anode material, which comprises titanium dioxide as a raw material comprising the following steps:
  • the sheet pressed in the step (1) is a positive electrode, and the lithium sheet is a negative electrode assembled into a battery, and the amount of electricity required for lithium insertion is calculated according to the mass of the titanium dioxide and the ratio of lithium to titanium, and discharged on the discharge instrument;
  • the lithium intercalated titanium oxide is taken out and subjected to high temperature annealing to obtain a lithium titanate product.
  • the titanium dioxide is a nanoparticle with a particle size of 25 nm; the large particle increases the difficulty of lithium ion insertion. It can cause uneven lithium intercalation, reduce purity, high cost of small particles, and difficult operation. 25nm titanium dioxide particles are mature commercial materials and are the best overall performance.
  • the binder is polyvinylidene fluoride or polytetrafluoroethylene
  • the conductive agent is one or more of acetylene black, Super P, Ketjen black, KS-6, carbon nanotubes, and graphene.
  • the binder ensures the strength of the tablet, but too much will affect the conductivity of the tablet and increase the cost, too little to achieve bonding, and the mass fraction of 5 to 20% is the optimum ratio.
  • the conductive agent ensures the conductivity of the tablet during the discharge process, but too much will affect the difficulty of the tablet and increase the cost, too little effect is not obvious, the mass fraction is 5-20% is the optimal ratio; the titanium dioxide, sticky
  • the mass ratio of the binder and the conductive agent is 60-90:5-20:5-20, and the mixing method of the three methods is a ball milling method or a grinding method.
  • the molar ratio of lithium to titanium is 4:5, and the calculation formula for the amount of electricity required for embedding a certain amount of titanium dioxide into the corresponding amount of lithium is:
  • m is the number of titanium dioxide
  • M is the molecular weight of titanium dioxide
  • the lithium insertion amount of titanium dioxide is just 0.8 at the time of discharge;
  • the discharge instrument is a battery tester or an electrochemical workstation to select a low-range battery test under the condition of satisfying the range.
  • the discharge current is controlled below 0.1C to ensure that lithium ions can be uniformly embedded in the titanium dioxide.
  • the annealing temperature is 400-1000 ° C, preferably 400-700 ° C, further preferably 550 ° C; annealing time is 5-24 h, the purpose is to utilize oxygen in the air, lithium titanium oxide recombination Lithium titanate is formed.
  • the product prepared by the method of the invention is applied to the preparation of a CR2032 type button battery, characterized in that lithium titanate is mixed with acetylene black and polyvinylidene fluoride in a mass ratio of 80:10:10, and 1-methyl group is added.
  • -2-pyrrolidone The mixture was prepared into a slurry, uniformly coated on an aluminum foil, dried at 80 ° C for 6 hours, vacuum dried at 120 ° C for 12 hours to obtain a pole piece, and the pole piece was transferred to a glove box with metallic lithium. Assemble the pole into a CR2032 button battery.
  • the invention prepares a lithium titanate material by electrochemical and high-temperature treatment, and the prepared lithium titanate has high purity, the assembled battery has high specific capacity and excellent cycle performance.
  • the invention can accurately control the ratio of lithium to titanium, and the raw material is cheap. Only the commercial nano titanium dioxide material is needed, and lithium titanate can be obtained by electrochemical and high temperature treatment. According to the quality of the titanium dioxide, the controlled discharge amount can be accurately controlled and embedded. The amount of lithium ensures the purity of lithium titanate.
  • the battery prepared according to the present invention has a first discharge specific capacity of 160 mAh/g, and the cycle capacity is not attenuated at a large rate.
  • Example 1 is an XRD chart of a lithium titanate material prepared in Example 1 of the present invention.
  • Example 2 is a graph showing the rate performance test of a lithium ion battery made of a lithium titanate material prepared in Example 2 of the present invention
  • Example 3 is a test chart of charge and discharge cycle performance of a lithium ion battery made of a lithium titanate material prepared in Example 1 of the present invention
  • Example 4 is a graph showing the charge and discharge cycle performance of a lithium ion battery made of a lithium titanate material prepared in Example 4 of the present invention.
  • the prepared button battery was placed on a battery tester and discharged at a constant current of 0.05 C to a capacity of 42.88 mAh.
  • the lithium intercalated titanium oxide was taken out and incubated at 550 ° C for 15 hours in a muffle furnace to obtain lithium titanate.
  • the obtained lithium titanate is mixed with the conductive agent acetylene black and the binder PVDF at a mass ratio of 80:10:10, and NMP (1-methyl-2-pyrrolidone) is added to prepare a slurry, which is uniformly coated on the aluminum foil. After drying at 80 ° C for 6 hours and vacuum drying at 120 ° C for 12 hours to obtain pole pieces, the pole pieces were transferred into a glove box, and metal lithium was used as a counter electrode to assemble a CR2032 type button battery.
  • the first discharge specific capacity at the 0.2C rate reached 175.4 mAh/g, and after 1 time, the 1C rate was 300 cycles and still had 155.5 mAh/g.
  • the prepared button battery was placed on a battery tester and discharged at a constant current of 0.05 C to a capacity of 32.16 mAh.
  • the lithium-deposited titanium oxide was taken out and kept at 750 ° C for 5 hours in a muffle furnace to obtain lithium titanate.
  • the obtained lithium titanate was mixed with the conductive agent acetylene black and the binder PVDF at a mass ratio of 80:10:10, and the mixture was prepared into a slurry by adding NMP, uniformly coated on an aluminum foil, and dried at 80 ° C for 6 hours, 120 ° C.
  • the pole piece was obtained by vacuum drying for 12 hours, and the pole piece was transferred into a glove box, and a lithium battery was used as a counter electrode to assemble a CR2032 type button battery.
  • the first discharge specific capacity at 0.2C rate reached 178.7mAh/g, and after 2 times, the 1C rate, 3C rate and 6C rate were still 134.5mAh/g after 20 cycles.
  • the prepared button battery was placed on a battery tester and discharged at a constant current of 0.05 C to a capacity of 48.24 mAh.
  • the lithium intercalated titanium dioxide was taken out and kept at 400 ° C for 24 hours in a muffle furnace to obtain lithium titanate.
  • the obtained lithium titanate was mixed with the conductive agent acetylene black and the binder PVDF at a mass ratio of 80:10:10, and the mixture was prepared into a slurry by adding NMP, uniformly coated on an aluminum foil, and dried at 80 ° C for 6 hours, 120 ° C.
  • the pole piece was obtained by vacuum drying for 12 hours, and the pole piece was transferred into a glove box, and a lithium battery was used as a counter electrode to assemble a CR2032 type button battery.
  • the first discharge specific capacity at the 0.2C rate reached 184.1 mAh/g, and after 2 cycles, the 1C rate, 3C rate and 6C rate were still 84.1 mAh/g after 20 cycles.
  • the prepared button battery was placed on a battery tester and discharged at a constant current of 0.05 C to a capacity of 42.88 mAh.
  • the lithium-deposited titanium oxide was taken out and kept at 1000 ° C for 5 hours in a muffle furnace to obtain lithium titanate.
  • the obtained lithium titanate was mixed with the conductive agent acetylene black and the binder PVDF at a mass ratio of 80:10:10, and the mixture was prepared into a slurry by adding NMP, uniformly coated on an aluminum foil, and dried at 80 ° C for 6 hours, 120 ° C.
  • the pole piece was obtained by vacuum drying for 12 hours, and the pole piece was transferred into a glove box, and a lithium battery was used as a counter electrode to assemble a CR2032 type button battery.
  • the first discharge specific capacity at the 0.2C rate reached 177.3 mAh/g, and after 2 cycles, the 1C rate still had 129.7 mAh/g after 100 cycles.

Abstract

The present invention falls within the field of lithium ion batteries, and particularly discloses a method for preparing a high-purity lithium titanate negative electrode material and use thereof. The preparation method with titanium dioxide as a raw material is characterized by uniformly mixing titanium dioxide, a binder and a conductive agent, and then pressing same into a sheet; assembling a battery using the pressed sheet as a positive electrode and a lithium sheet as a negative electrode, calculating the electric quantity required by lithium intercalation according to the mass of the titanium dioxide and the lithium-titanium ratio, and discharging on a discharging apparatus; and after the completion of the discharging, taking out the lithium-intercalated titanium dioxide, and carrying out a high-temperature annealing treatment to obtain a lithium titanate product. The lithium titanate material is prepared by an electrochemical treatment and a high-temperature treatment. The prepared lithium titanate has a high purity. The assembled battery has a high specific capacity and excellent cycle performance.

Description

一种高纯度钛酸锂负极材料的制备方法及其应用Preparation method of high-purity lithium titanate anode material and application thereof (一)技术领域(1) Technical field
本发明属于锂离子电池领域，特别涉及一种高纯度钛酸锂负极材料的制备方法及其应用。The invention belongs to the field of lithium ion batteries, and in particular relates to a preparation method and application of a high-purity lithium titanate anode material.
(二)背景技术(2) Background technology
钛酸锂作为锂离子电池负极材料引起了广泛关注，钛酸锂属于尖晶石型结构，其结构可以为锂离子的扩散提供三维的通道，在锂离子的嵌入和脱出过程中，钛酸锂的晶胞参数和体积变化很小，被称为“零应变”材料。极低的体积变化和充足锂离子孔道，使得钛酸锂具有极其优良的循环性能和大倍率充放电性能。Lithium titanate has attracted extensive attention as a negative electrode material for lithium ion batteries. Lithium titanate is a spinel-type structure, and its structure can provide three-dimensional channels for the diffusion of lithium ions. In the process of lithium ion insertion and extraction, lithium titanate The unit cell parameters and volume change are small and are referred to as "zero strain" materials. Extremely low volume changes and sufficient lithium ion channels make lithium titanate extremely excellent cycle performance and high rate charge and discharge performance.
目前钛酸锂常见的制备方法主要有固相反应法、溶胶凝胶法和水热反应法等。固相法工艺简单，但往往难以保证混料均匀，且长时间高温煅烧导致能耗较高，锂盐在高温下挥发致使产物纯度较低；溶胶凝胶法产品纯度高，颗粒大小控制好，但使用高成本的钛酸酯为原料导致成本很高，主要用于实验室研究；水热法产物纯度高，成本低，但使用高温高压的体系，设备要求高，投入较大。At present, the common preparation methods of lithium titanate mainly include solid phase reaction method, sol-gel method and hydrothermal reaction method. The solid phase process is simple, but it is often difficult to ensure uniform mixing, and high-temperature calcination results in high energy consumption. The lithium salt volatilizes at high temperature, resulting in low purity of the product; the sol-gel method has high purity and good particle size control. However, the use of high-cost titanate as a raw material leads to high cost, mainly used in laboratory research; hydrothermal method products have high purity and low cost, but the use of high temperature and high pressure systems requires high equipment and large investment.
电化学方法简单，能源清洁，成本低，是一种理想的合成方法。中国专利CN103290426A公开了“一种钛酸锂的制备方法”，采用二氧化钛为阴极，石墨为阳极，熔融的碱金属卤化物为电解质，高温下电解，退火后得到钛酸锂。此方法可以得到较纯的钛酸锂，但生产过程需要高温熔融状态，钛锂比难以精确控制阻碍了其工业应用。The electrochemical method is simple, the energy is clean, and the cost is low, which is an ideal synthetic method. Chinese Patent No. CN103290426A discloses "a preparation method of lithium titanate", which uses titanium dioxide as a cathode, graphite as an anode, molten alkali metal halide as an electrolyte, electrolysis at a high temperature, and anodized to obtain lithium titanate. This method can obtain relatively pure lithium titanate, but the production process requires a high-temperature molten state, and it is difficult to accurately control the titanium-lithium ratio to hinder its industrial application.
(三)发明内容(3) Invention content
本发明为了弥补现有技术的不足，提供了一种可规模化生产、电池性能良好的高纯度钛酸锂负极材料的制备方法及其应用。In order to make up for the deficiencies of the prior art, the present invention provides a preparation method and application of a high-purity lithium titanate negative electrode material which can be mass-produced and has good battery performance.
本发明是通过如下技术方案实现的：The invention is achieved by the following technical solutions:
一种高纯度钛酸锂负极材料的制备方法，以二氧化钛为原料，包括如下步骤：A method for preparing a high-purity lithium titanate anode material, which comprises titanium dioxide as a raw material, comprising the following steps:
(1)将二氧化钛、粘结剂、导电剂混合均匀后，压制成片；(1) mixing titanium dioxide, a binder, and a conductive agent, and then pressing into a tablet;
(2)以步骤(1)中压制的片为正极，锂片为负极组装成电池，根据二氧化钛的质量和锂钛的比例计算嵌锂需要的电量，在放电仪器上放电；(2) The sheet pressed in the step (1) is a positive electrode, and the lithium sheet is a negative electrode assembled into a battery, and the amount of electricity required for lithium insertion is calculated according to the mass of the titanium dioxide and the ratio of lithium to titanium, and discharged on the discharge instrument;
(3)放电完毕后，取出嵌锂的二氧化钛，高温退火处理得到钛酸锂产品。(3) After the discharge is completed, the lithium intercalated titanium oxide is taken out and subjected to high temperature annealing to obtain a lithium titanate product.
本发明的更优技术方案为：A more preferred technical solution of the present invention is:
所述二氧化钛为纳米颗粒，颗粒大小为25nm；大颗粒增加了锂离子嵌入的难度，可 能造成嵌锂不均匀，降低纯度，小颗粒的成本较高，操作困难，25nm的二氧化钛颗粒是目前成熟的商业材料，是综合性能最优的尺寸。The titanium dioxide is a nanoparticle with a particle size of 25 nm; the large particle increases the difficulty of lithium ion insertion. It can cause uneven lithium intercalation, reduce purity, high cost of small particles, and difficult operation. 25nm titanium dioxide particles are mature commercial materials and are the best overall performance.
所述粘结剂为聚偏氟乙烯或聚四氟乙烯，导电剂为乙炔黑、Super P、科琴黑、KS-6、碳纳米管和石墨烯中的一种或多种。粘结剂保证了压片的强度，但太多会影响压片的导电性并增加成本，太少起不到粘结作用，质量分数为5～20％是最佳比例。导电剂保证了压片在放电过程中的导电性，但太多会影响制片的难度并增加成本，太少作用不明显，质量分数为5～20％是最佳比例；所述二氧化钛、粘结剂、导电剂的质量配比为60-90:5-20:5-20，三者的混合方法为球磨法或研磨法。The binder is polyvinylidene fluoride or polytetrafluoroethylene, and the conductive agent is one or more of acetylene black, Super P, Ketjen black, KS-6, carbon nanotubes, and graphene. The binder ensures the strength of the tablet, but too much will affect the conductivity of the tablet and increase the cost, too little to achieve bonding, and the mass fraction of 5 to 20% is the optimum ratio. The conductive agent ensures the conductivity of the tablet during the discharge process, but too much will affect the difficulty of the tablet and increase the cost, too little effect is not obvious, the mass fraction is 5-20% is the optimal ratio; the titanium dioxide, sticky The mass ratio of the binder and the conductive agent is 60-90:5-20:5-20, and the mixing method of the three methods is a ball milling method or a grinding method.
步骤(2)中，锂钛的摩尔比为4:5，则一定质量二氧化钛嵌入对应量锂所需要的电量计算公式为：
Figure PCTCN2016084173-appb-000001
其中m为二氧化钛的克数，M为二氧化钛的分子量，放电到此时二氧化钛的嵌锂量恰好为0.8；放电仪器为电池测试仪或电化学工作站在满足量程的条件下尽量选择低量程的电池测试仪，放电电流控制在0.1C以下，保证锂离子可以均匀地嵌入到二氧化钛中。In the step (2), the molar ratio of lithium to titanium is 4:5, and the calculation formula for the amount of electricity required for embedding a certain amount of titanium dioxide into the corresponding amount of lithium is:
Figure PCTCN2016084173-appb-000001
Where m is the number of titanium dioxide, M is the molecular weight of titanium dioxide, and the lithium insertion amount of titanium dioxide is just 0.8 at the time of discharge; the discharge instrument is a battery tester or an electrochemical workstation to select a low-range battery test under the condition of satisfying the range. The discharge current is controlled below 0.1C to ensure that lithium ions can be uniformly embedded in the titanium dioxide.
步骤(3)中，所述退火温度为400-1000℃，优选的是400-700℃，进一步优选的是550℃；退火时间为5-24h，目的是利用空气中的氧，锂钛氧重组形成钛酸锂。In the step (3), the annealing temperature is 400-1000 ° C, preferably 400-700 ° C, further preferably 550 ° C; annealing time is 5-24 h, the purpose is to utilize oxygen in the air, lithium titanium oxide recombination Lithium titanate is formed.
利用本发明所述方法制备所得产品应用于CR2032型纽扣电池的制备，其特征在于：将钛酸锂与乙炔黑、聚偏氟乙烯按80:10:10的质量比混合，加入1-甲基-2-吡咯烷酮将混合物调制成浆料，均匀涂覆在铝箔上，于80℃下干燥6小时，120℃下真空干燥12小时制得极片，将极片转移到手套箱中，以金属锂为对极组装成CR2032型纽扣电池。The product prepared by the method of the invention is applied to the preparation of a CR2032 type button battery, characterized in that lithium titanate is mixed with acetylene black and polyvinylidene fluoride in a mass ratio of 80:10:10, and 1-methyl group is added. -2-pyrrolidone The mixture was prepared into a slurry, uniformly coated on an aluminum foil, dried at 80 ° C for 6 hours, vacuum dried at 120 ° C for 12 hours to obtain a pole piece, and the pole piece was transferred to a glove box with metallic lithium. Assemble the pole into a CR2032 button battery.
本发明通过电化学和高温处理制备了钛酸锂材料，制备的钛酸锂纯度高，组装的电池比容量高，循环性能优异。The invention prepares a lithium titanate material by electrochemical and high-temperature treatment, and the prepared lithium titanate has high purity, the assembled battery has high specific capacity and excellent cycle performance.
本发明可以精确控制锂钛比例，原料便宜，只需要使用商业化的纳米二氧化钛材料，通过电化学和高温处理两个步骤就可以得到钛酸锂，根据二氧化钛的质量，控制放电量可以精确控制嵌入锂的量，保证了钛酸锂的纯度。按本发明制备的电池，首次放电比容量达到了160mAh/g，较大倍率下循环容量不衰减。The invention can accurately control the ratio of lithium to titanium, and the raw material is cheap. Only the commercial nano titanium dioxide material is needed, and lithium titanate can be obtained by electrochemical and high temperature treatment. According to the quality of the titanium dioxide, the controlled discharge amount can be accurately controlled and embedded. The amount of lithium ensures the purity of lithium titanate. The battery prepared according to the present invention has a first discharge specific capacity of 160 mAh/g, and the cycle capacity is not attenuated at a large rate.
(四)附图说明(4) Description of the drawings
下面结合附图对本发明作进一步的说明。The invention will now be further described with reference to the accompanying drawings.
图1为本发明实施例1制备的钛酸锂材料的XRD图；1 is an XRD chart of a lithium titanate material prepared in Example 1 of the present invention;
图2为本发明实施例2制备的钛酸锂材料做成的锂离子电池的倍率性能测试图； 2 is a graph showing the rate performance test of a lithium ion battery made of a lithium titanate material prepared in Example 2 of the present invention;
图3为本发明实施例1制备的钛酸锂材料做成的锂离子电池的充放电循环性能测试图；3 is a test chart of charge and discharge cycle performance of a lithium ion battery made of a lithium titanate material prepared in Example 1 of the present invention;
图4为本发明实施例4制备的钛酸锂材料做成的锂离子电池的充放电循环性能测试图。4 is a graph showing the charge and discharge cycle performance of a lithium ion battery made of a lithium titanate material prepared in Example 4 of the present invention.
(五)具体实施方式(5) Specific implementation methods
下面通过具体实施方案对本发明作进一步详细描述，但这些实施实例仅在于举例说明，并不对本发明的范围进行限定。The invention is further described in detail below by way of specific examples, but these examples are only intended to be illustrative, and not to limit the scope of the invention.
实施例1：Example 1:
称取1.6g二氧化钛、0.2g PVDF和0.2g乙炔黑，研钵中研磨半小时充分混合均匀，取0.2g混合物放入模具，20MPa压强下压制1分钟成片。将压片做正极，选用CR2032纽扣电池壳，按照负极壳、弹簧片、垫片、锂片、隔膜、正极、正极壳的顺序组装电池，滴加5滴锂离子电池电解液，用封口机封口制备纽扣电池。将制备的纽扣电池放到电池测试仪上，0.05C恒流放电至42.88mAh的容量。取出嵌锂后的二氧化钛，马弗炉中550℃保温15小时得到钛酸锂。1.6 g of titanium dioxide, 0.2 g of PVDF and 0.2 g of acetylene black were weighed, thoroughly mixed in a mortar for half an hour, and 0.2 g of the mixture was placed in a mold, and pressed under a pressure of 20 MPa for 1 minute to form a tablet. The positive electrode is pressed, the CR2032 button battery case is selected, the battery is assembled in the order of the negative electrode case, the spring piece, the gasket, the lithium piece, the separator, the positive electrode and the positive electrode case, and 5 drops of lithium ion battery electrolyte are added dropwise, and the sealing machine is sealed with a sealing machine. Prepare button batteries. The prepared button battery was placed on a battery tester and discharged at a constant current of 0.05 C to a capacity of 42.88 mAh. The lithium intercalated titanium oxide was taken out and incubated at 550 ° C for 15 hours in a muffle furnace to obtain lithium titanate.
将所得的钛酸锂与导电剂乙炔黑、粘结剂PVDF按质量比80:10:10混合，加入NMP(1-甲基-2吡咯烷酮)将混合物调制成浆料，均匀涂覆在铝箔上，80℃干燥6小时，120℃真空干燥12小时制得极片，将极片转移到手套箱中，以金属锂为对极组装成CR2032型纽扣电池。The obtained lithium titanate is mixed with the conductive agent acetylene black and the binder PVDF at a mass ratio of 80:10:10, and NMP (1-methyl-2-pyrrolidone) is added to prepare a slurry, which is uniformly coated on the aluminum foil. After drying at 80 ° C for 6 hours and vacuum drying at 120 ° C for 12 hours to obtain pole pieces, the pole pieces were transferred into a glove box, and metal lithium was used as a counter electrode to assemble a CR2032 type button battery.
按本实例制作的电池，0.2C倍率首次放电比容量达到了175.4mAh/g，2次后1C倍率300次循环后仍然拥有155.5mAh/g。According to the battery produced in this example, the first discharge specific capacity at the 0.2C rate reached 175.4 mAh/g, and after 1 time, the 1C rate was 300 cycles and still had 155.5 mAh/g.
实施例2：Example 2:
称取12g二氧化钛、4g PVDF、2g乙炔黑和2g Super P，放入100ml球磨罐，球料比为3:1，研磨2小时充分混合均匀，取0.2g混合物放入模具，20MPa压强下压制1分钟成片。将压片做正极，选用CR2032纽扣电池壳，按照负极壳、弹簧片、垫片、锂片、隔膜、正极、正极壳的顺序组装电池，滴加5滴锂离子电池电解液，用封口机封口制备纽扣电池。将制备的纽扣电池放到电池测试仪上，0.05C恒流放电至32.16mAh的容量。取出嵌锂后的二氧化钛，马弗炉中750℃保温5小时得到钛酸锂。Weigh 12g titanium dioxide, 4g PVDF, 2g acetylene black and 2g Super P, put into a 100ml ball mill tank, the ball to material ratio is 3:1, grind for 2 hours, mix well, take 0.2g mixture into the mold, press under 20MPa pressure 1 Minutes into pieces. The positive electrode is pressed, the CR2032 button battery case is selected, the battery is assembled in the order of the negative electrode case, the spring piece, the gasket, the lithium piece, the separator, the positive electrode and the positive electrode case, and 5 drops of lithium ion battery electrolyte are added dropwise, and the sealing machine is sealed with a sealing machine. Prepare button batteries. The prepared button battery was placed on a battery tester and discharged at a constant current of 0.05 C to a capacity of 32.16 mAh. The lithium-deposited titanium oxide was taken out and kept at 750 ° C for 5 hours in a muffle furnace to obtain lithium titanate.
将所得的钛酸锂与导电剂乙炔黑、粘结剂PVDF按质量比80:10:10混合，加入NMP将混合物调制成浆料，均匀涂覆在铝箔上，80℃干燥6小时，120℃真空干燥12小时制得极片，将极片转移到手套箱中，以金属锂为对极组装成CR2032型纽扣电池。 The obtained lithium titanate was mixed with the conductive agent acetylene black and the binder PVDF at a mass ratio of 80:10:10, and the mixture was prepared into a slurry by adding NMP, uniformly coated on an aluminum foil, and dried at 80 ° C for 6 hours, 120 ° C. The pole piece was obtained by vacuum drying for 12 hours, and the pole piece was transferred into a glove box, and a lithium battery was used as a counter electrode to assemble a CR2032 type button battery.
按本实例制作的电池，0.2C倍率首次放电比容量达到了178.7mAh/g，2次后1C倍率、3C倍率和6C倍率分别循环20次后仍然拥有134.5mAh/g。According to the battery produced in this example, the first discharge specific capacity at 0.2C rate reached 178.7mAh/g, and after 2 times, the 1C rate, 3C rate and 6C rate were still 134.5mAh/g after 20 cycles.
实施例3：Example 3:
称取1.8g二氧化钛、0.1g PVDF和0.1g碳纳米管，研钵中研磨半小时充分混合均匀，取0.2g混合物放入模具，20MPa压强下压制1分钟成片。将压片做正极，选用CR2032纽扣电池壳，按照负极壳、弹簧片、垫片、锂片、隔膜、正极、正极壳的顺序组装电池，滴加5滴锂离子电池电解液，用封口机封口制备纽扣电池。将制备的纽扣电池放到电池测试仪上，0.05C恒流放电至48.24mAh的容量。取出嵌锂后的二氧化钛，马弗炉中400℃保温24小时得到钛酸锂。1.8 g of titanium dioxide, 0.1 g of PVDF and 0.1 g of carbon nanotubes were weighed, thoroughly mixed in a mortar for half an hour, and 0.2 g of the mixture was placed in a mold and pressed at 20 MPa for 1 minute to form a tablet. The positive electrode is pressed, the CR2032 button battery case is selected, the battery is assembled in the order of the negative electrode case, the spring piece, the gasket, the lithium piece, the separator, the positive electrode and the positive electrode case, and 5 drops of lithium ion battery electrolyte are added dropwise, and the sealing machine is sealed with a sealing machine. Prepare button batteries. The prepared button battery was placed on a battery tester and discharged at a constant current of 0.05 C to a capacity of 48.24 mAh. The lithium intercalated titanium dioxide was taken out and kept at 400 ° C for 24 hours in a muffle furnace to obtain lithium titanate.
将所得的钛酸锂与导电剂乙炔黑、粘结剂PVDF按质量比80:10:10混合，加入NMP将混合物调制成浆料，均匀涂覆在铝箔上，80℃干燥6小时，120℃真空干燥12小时制得极片，将极片转移到手套箱中，以金属锂为对极组装成CR2032型纽扣电池。The obtained lithium titanate was mixed with the conductive agent acetylene black and the binder PVDF at a mass ratio of 80:10:10, and the mixture was prepared into a slurry by adding NMP, uniformly coated on an aluminum foil, and dried at 80 ° C for 6 hours, 120 ° C. The pole piece was obtained by vacuum drying for 12 hours, and the pole piece was transferred into a glove box, and a lithium battery was used as a counter electrode to assemble a CR2032 type button battery.
按本实例制作的电池，0.2C倍率首次放电比容量达到了184.1mAh/g，2次后1C倍率、3C倍率和6C倍率分别循环20次后仍然拥有84.1mAh/g。According to the battery produced in this example, the first discharge specific capacity at the 0.2C rate reached 184.1 mAh/g, and after 2 cycles, the 1C rate, 3C rate and 6C rate were still 84.1 mAh/g after 20 cycles.
实施例4：Example 4:
称取1.6g二氧化钛、0.2g PTFE、0.1g碳纳米管和0.1g石墨烯，研钵中研磨半小时充分混合均匀，取0.2g混合物放入模具，20MPa压强下压制1分钟成片。将压片做正极，选用CR2032纽扣电池壳，按照负极壳、弹簧片、垫片、锂片、隔膜、正极、正极壳的顺序组装电池，滴加5滴锂离子电池电解液，用封口机封口制备纽扣电池。将制备的纽扣电池放到电池测试仪上，0.05C恒流放电至42.88mAh的容量。取出嵌锂后的二氧化钛，马弗炉中1000℃保温5小时得到钛酸锂。1.6 g of titanium dioxide, 0.2 g of PTFE, 0.1 g of carbon nanotubes and 0.1 g of graphene were weighed, thoroughly mixed in a mortar for half an hour, and 0.2 g of the mixture was placed in a mold, and pressed at 20 MPa for 1 minute to form a tablet. The positive electrode is pressed, the CR2032 button battery case is selected, the battery is assembled in the order of the negative electrode case, the spring piece, the gasket, the lithium piece, the separator, the positive electrode and the positive electrode case, and 5 drops of lithium ion battery electrolyte are added dropwise, and the sealing machine is sealed with a sealing machine. Prepare button batteries. The prepared button battery was placed on a battery tester and discharged at a constant current of 0.05 C to a capacity of 42.88 mAh. The lithium-deposited titanium oxide was taken out and kept at 1000 ° C for 5 hours in a muffle furnace to obtain lithium titanate.
将所得的钛酸锂与导电剂乙炔黑、粘结剂PVDF按质量比80:10:10混合，加入NMP将混合物调制成浆料，均匀涂覆在铝箔上，80℃干燥6小时，120℃真空干燥12小时制得极片，将极片转移到手套箱中，以金属锂为对极组装成CR2032型纽扣电池。The obtained lithium titanate was mixed with the conductive agent acetylene black and the binder PVDF at a mass ratio of 80:10:10, and the mixture was prepared into a slurry by adding NMP, uniformly coated on an aluminum foil, and dried at 80 ° C for 6 hours, 120 ° C. The pole piece was obtained by vacuum drying for 12 hours, and the pole piece was transferred into a glove box, and a lithium battery was used as a counter electrode to assemble a CR2032 type button battery.
按本实例制作的电池，0.2C倍率首次放电比容量达到了177.3mAh/g，2次后1C倍率100次循环后仍然拥有129.7mAh/g。 According to the battery produced in this example, the first discharge specific capacity at the 0.2C rate reached 177.3 mAh/g, and after 2 cycles, the 1C rate still had 129.7 mAh/g after 100 cycles.

Claims (10)

  1. 一种高纯度钛酸锂负极材料的制备方法，以二氧化钛为原料，其特征为，包括如下步骤：(1)将二氧化钛、粘结剂、导电剂混合均匀后，压制成片；(2)以步骤(1)中压制的片为正极，锂片为负极组装成电池，根据二氧化钛的质量和锂钛的比例计算嵌锂需要的电量，在放电仪器上放电；(3)放电完毕后，取出嵌锂的二氧化钛，高温退火处理得到钛酸锂产品。A method for preparing a high-purity lithium titanate negative electrode material, which comprises titanium dioxide as a raw material, and comprises the following steps: (1) mixing titanium dioxide, a binder and a conductive agent uniformly, and then pressing into a tablet; (2) The sheet pressed in the step (1) is a positive electrode, and the lithium sheet is a negative electrode assembled into a battery, and the amount of electricity required for lithium insertion is calculated according to the mass of the titanium dioxide and the ratio of lithium to titanium, and discharged on the discharge instrument; (3) after the discharge is completed, the insertion is performed. Lithium titanium dioxide, high temperature annealing treatment to obtain lithium titanate products.
  2. 根据权利要求1所述的高纯度钛酸锂负极材料的制备方法，其特征在于：所述二氧化钛为纳米颗粒，颗粒大小为25nm。The method for producing a high-purity lithium titanate negative electrode material according to claim 1, wherein the titanium dioxide is a nanoparticle having a particle size of 25 nm.
  3. 根据权利要求1所述的高纯度钛酸锂负极材料的制备方法，其特征在于：所述粘结剂为聚偏氟乙烯或聚四氟乙烯，导电剂为乙炔黑、Super P、科琴黑、KS-6、碳纳米管和石墨烯中的一种或多种。The method for preparing a high-purity lithium titanate negative electrode material according to claim 1, wherein the binder is polyvinylidene fluoride or polytetrafluoroethylene, and the conductive agent is acetylene black, Super P, and Ketchen black. One or more of KS-6, carbon nanotubes, and graphene.
  4. 根据权利要求1所述的高纯度钛酸锂负极材料的制备方法，其特征在于：步骤(1)中，所述二氧化钛、粘结剂、导电剂的质量配比为60-90:5-20:5-20，三者的混合方法为球磨法或研磨法。The method for preparing a high-purity lithium titanate negative electrode material according to claim 1, wherein in the step (1), the mass ratio of the titanium dioxide, the binder and the conductive agent is 60-90: 5-20. : 5-20, the mixing method of the three is a ball milling method or a grinding method.
  5. 根据权利要求1所述的高纯度钛酸锂负极材料的制备方法，其特征在于：步骤(2)中，锂钛的摩尔比为4:5，放电仪器为电池测试仪或电化学工作站，放电电流在0.1C以下。The method for preparing a high-purity lithium titanate negative electrode material according to claim 1, wherein in the step (2), the molar ratio of lithium to titanium is 4:5, and the discharge device is a battery tester or an electrochemical workstation, and the discharge is The current is below 0.1C.
  6. 根据权利要求1所述的高纯度钛酸锂负极材料的制备方法，其特征在于：步骤(3)中，所述退火温度为400-1000℃，退火时间为5-24h。The method for preparing a high-purity lithium titanate negative electrode material according to claim 1, wherein in the step (3), the annealing temperature is 400-1000 ° C, and the annealing time is 5-24 h.
  7. 根据权利要求6所述的高纯度钛酸锂负极材料的制备方法，其特征在于：所述退火温度为400-700℃。The method for producing a high-purity lithium titanate negative electrode material according to claim 6, wherein the annealing temperature is 400 to 700 °C.
  8. 根据权利要求6或7所述的高纯度钛酸锂负极材料的制备方法，其特征在于：所述退火温度为550℃。The method for producing a high-purity lithium titanate negative electrode material according to claim 6 or 7, wherein the annealing temperature is 550 °C.
  9. 利用权利要求1所述方法制备所得产品应用于CR2032型纽扣电池的制备。The resulting product was prepared by the method of claim 1 for use in the preparation of a CR2032 type coin cell.
  10. 根据权利要求9所述的CR2032型纽扣电池的制备，其特征在于：将钛酸锂与乙炔黑、聚偏氟乙烯按80:10:10的质量比混合，加入1-甲基-2-吡咯烷酮将混合物调制成浆料，均匀涂覆在铝箔上，于80℃下干燥6小时，120℃下真空干燥12小时制得极片，将极片转移到手套箱中，以金属锂为对极组装成CR2032型纽扣电池。 The invention relates to the preparation of the CR2032 type button battery according to claim 9, characterized in that lithium titanate is mixed with acetylene black and polyvinylidene fluoride in a mass ratio of 80:10:10, and 1-methyl-2-pyrrolidone is added. The mixture was prepared into a slurry, uniformly coated on an aluminum foil, dried at 80 ° C for 6 hours, vacuum dried at 120 ° C for 12 hours to obtain a pole piece, and the pole piece was transferred to a glove box to be assembled with metal lithium as a counter electrode. Into the CR2032 button battery.
PCT/CN2016/084173 2015-06-15 2016-05-31 Method for preparing high-purity lithium titanate negative electrode material and use thereof WO2016202173A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510328775.6A CN105036182B (en) 2015-06-15 2015-06-15 A kind of preparation method and applications of high-purity lithium titanate anode material
CN201510328775.6 2015-06-15

Publications (1)

Publication Number Publication Date
WO2016202173A1 true WO2016202173A1 (en) 2016-12-22

Family

ID=54443234

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/084173 WO2016202173A1 (en) 2015-06-15 2016-05-31 Method for preparing high-purity lithium titanate negative electrode material and use thereof

Country Status (2)

Country Link
CN (1) CN105036182B (en)
WO (1) WO2016202173A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114142080A (en) * 2021-11-25 2022-03-04 深圳市瀚海龙科技有限公司 Ultra-capacity graphene battery and preparation method thereof
CN114335455A (en) * 2021-12-06 2022-04-12 电子科技大学长三角研究院(湖州) Method for precisely fluorinating soft carbon with adjustable crystallinity and research on performance of primary battery

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105036182B (en) * 2015-06-15 2017-03-08 山东玉皇新能源科技有限公司 A kind of preparation method and applications of high-purity lithium titanate anode material
CN105047989B (en) * 2015-07-09 2017-07-11 山东玉皇新能源科技有限公司 A kind of electrochemical preparation method of Ca-Ti ore type solid electrolyte lithium lanthanum titanium oxide
CN105514416A (en) * 2016-01-25 2016-04-20 山东玉皇新能源科技有限公司 Preparing method and application of high-purity lithium manganate anode material
CN105731549A (en) * 2016-01-25 2016-07-06 山东玉皇新能源科技有限公司 Preparation method and application of high-purity lithium cobalt oxide cathode material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101488584A (en) * 2009-03-06 2009-07-22 清华大学 Asymmetric lithium iron phosphate cell using lithium titanate as main active substance of negative pole
CN103915262A (en) * 2013-01-04 2014-07-09 深圳清华大学研究院 Method for lithium pre-embedment of negative electrode of lithium ion capacitor
CN105036182A (en) * 2015-06-15 2015-11-11 山东玉皇新能源科技有限公司 Preparation method and application of high-purity lithium titanate negative pole material

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4768901B2 (en) * 1999-06-03 2011-09-07 チタン工業株式会社 Lithium titanium composite oxide, method for producing the same, and use thereof
JP2011113795A (en) * 2009-11-26 2011-06-09 Nippon Chem Ind Co Ltd Manufacturing method of lithium titanate for lithium secondary battery active material
CN102820459A (en) * 2012-07-20 2012-12-12 合肥国轩高科动力能源有限公司 Preparation method for lithium titanate material with high specific energy from mesoporous titanium dioxide
CN103682332B (en) * 2012-09-26 2016-03-02 华为技术有限公司 Compound negative material of a kind of lithium ion battery and preparation method thereof and lithium ion battery
CN103290426B (en) * 2013-07-12 2015-07-01 广州有色金属研究院 Preparation method of lithium titanate
CN104091939A (en) * 2014-06-30 2014-10-08 北京工业大学 Hydrothermal synthesis preparation method for spherical Li4Ti5O12

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101488584A (en) * 2009-03-06 2009-07-22 清华大学 Asymmetric lithium iron phosphate cell using lithium titanate as main active substance of negative pole
CN103915262A (en) * 2013-01-04 2014-07-09 深圳清华大学研究院 Method for lithium pre-embedment of negative electrode of lithium ion capacitor
CN105036182A (en) * 2015-06-15 2015-11-11 山东玉皇新能源科技有限公司 Preparation method and application of high-purity lithium titanate negative pole material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114142080A (en) * 2021-11-25 2022-03-04 深圳市瀚海龙科技有限公司 Ultra-capacity graphene battery and preparation method thereof
CN114142080B (en) * 2021-11-25 2024-04-05 东莞市茂盛新能源科技有限公司 Super-capacity graphene battery and preparation method thereof
CN114335455A (en) * 2021-12-06 2022-04-12 电子科技大学长三角研究院(湖州) Method for precisely fluorinating soft carbon with adjustable crystallinity and research on performance of primary battery
CN114335455B (en) * 2021-12-06 2023-11-10 电子科技大学长三角研究院(湖州) Method for precisely fluorinating soft carbon with adjustable crystallinity and primary battery performance research

Also Published As

Publication number Publication date
CN105036182A (en) 2015-11-11
CN105036182B (en) 2017-03-08

Similar Documents

Publication Publication Date Title
WO2016202173A1 (en) Method for preparing high-purity lithium titanate negative electrode material and use thereof
Zhang et al. Li4Ti5O12 prepared by a modified citric acid sol–gel method for lithium-ion battery
WO2018090956A1 (en) Positive electrode material for high voltage lithium battery, battery, preparation method therefor and use thereof
CN105460917A (en) Nitrogen-doped carbon nanotube adopting hierarchical structure and preparation method
CN109873140B (en) Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material
CN102856553A (en) Preparation method of hydrothermal synthesis carbon coated lithium iron phosphate
CN105731549A (en) Preparation method and application of high-purity lithium cobalt oxide cathode material
CN113948681B (en) Biomass-based hard carbon compound composite material and preparation method and application thereof
CN105789615A (en) Modified lithium nickel cobalt manganese cathode material and preparation method thereof
CN114242968A (en) Carbon-coated sodium iron fluorophosphate material and preparation method and application thereof
CN105355892A (en) Preparation method of lithium ion battery cathode
TWI513084B (en) Process for producing lfmp/c composite material and use the same
Feng et al. Preparation of SnO2 nanoparticle and performance as lithium-ion battery anode
CN106207150A (en) A kind of atomizing freeze drying prepares the method for lithium cell negative pole material lithium titanate
WO2017005077A1 (en) Electrochemical preparation method for perovskite-type solid electrolyte lithium-lanthanum-titanium oxide compound
CN102070187B (en) Method for preparing spinel lithium titanate serving as negative material of lithium ion battery
CN104577090A (en) Method for preparing carbon and oxide composite modified lithium titanate material
CN107742710B (en) Preparation method of chromium-based lithium ion battery composite negative electrode material
CN103199248B (en) The preparation method of the coated niobium doped iron lithium phosphate of carbon-cobalt acid lithium composite positive pole
CN103117388B (en) Carbon coated ferriferrous oxide and preparation method thereof and the application in lithium ion battery
CN108288698A (en) A kind of preparation method of lithium iron phosphate positive material
CN107324379A (en) A kind of high power capacity lithium titanate material preparation method
CN106340625A (en) Preparation method of titanous self-doped titanium dioxide/carbon composite cathode material
CN107591530B (en) Modification method of lithium titanate negative electrode material
CN102723478A (en) Octahedral lithium manganate micron single crystal electrode material and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16810914

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16810914

Country of ref document: EP

Kind code of ref document: A1