WO2016023399A1 - Negative electrode active material, preparation method therefor, and lithium-ion battery - Google Patents

Negative electrode active material, preparation method therefor, and lithium-ion battery Download PDF

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WO2016023399A1
WO2016023399A1 PCT/CN2015/081508 CN2015081508W WO2016023399A1 WO 2016023399 A1 WO2016023399 A1 WO 2016023399A1 CN 2015081508 W CN2015081508 W CN 2015081508W WO 2016023399 A1 WO2016023399 A1 WO 2016023399A1
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active material
ion battery
manganese dioxide
negative electrode
electrode active
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French (fr)
Chinese (zh)
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陈敬波
王要武
何向明
徐盛明
赵骁
方谋
李建军
王莉
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江苏华东锂电技术研究院有限公司
清华大学
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Priority claimed from CN201410396821.1A external-priority patent/CN104183822B/en
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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
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

Definitions

  • the invention relates to a lithium ion battery anode active material, a preparation method thereof and a lithium ion battery.
  • transition metal oxides transition metal oxides
  • TMX transition metal oxides and other transition metal compounds
  • metal manganese oxides such as MnO, Mn 3 O 4 , Mn 2 O 3 , MnO 2 and the like are widely used in various types of electrochemical energy storage devices and have attracted wide interest.
  • Manganese oxides have numerous structures, and their electrochemical behavior is strongly dependent on oxidation states, nanostructures, and morphology. According to theoretical calculations, the theoretical lithium storage capacities of MnO, Mn 3 O 4 , Mn 2 O 3 , and MnO 2 are 755, 936, 1018, and 1232 mAh/g, respectively. Therefore, the specific capacity of MnO 2 is the highest.
  • MnO 2 has been widely used as a positive electrode material for primary lithium batteries in the field of batteries, and cannot be applied to secondary lithium ion batteries due to its low reversible capacity and poor cycle stability.
  • MnO 2 has a high theoretical specific capacity, and is rich in natural resources, there is a growing trend in the study as a lithium-ion battery anode material of MnO 2, however, is far MnO 2 electrochemical performance not satisfactory, The first reversible specific capacity is low, and it is even more unacceptable that the cycle performance is extremely poor, and the capacity decays rapidly after repeated cycles. Even researchers have doubted whether MnO 2 is electrochemically active and can be applied to secondary lithium-ion batteries.
  • the lithium ion battery anode active material has a high first reversible specific capacity and excellent cycle performance, and can be used for secondary Lithium Ion Battery.
  • a method for preparing a negative electrode active material comprising the steps of: mixing potassium permanganate with hydrogen chloride in water to form a solution; and hydrothermally reacting the solution in a hydrothermal kettle, wherein the solution in the hydrothermal kettle is high Potassium manganate, hydrogen chloride and water, the reaction temperature is 120 ° C ⁇ 160 ° C, the holding time is 0.5 hour ⁇ 2 hours, the manganese dioxide secondary ball, the manganese dioxide secondary ball from the plurality of manganese dioxide nanosheets composition.
  • An anode active material consisting of a manganese dioxide secondary sphere.
  • a lithium ion battery, the anode active material of the lithium ion battery being composed of a manganese dioxide secondary sphere.
  • the manganese dioxide secondary ball provided by the invention has simple preparation process and good electrical conductivity, and can be directly used as a negative active material of a lithium ion battery without being combined with a conductive material, and has a higher performance.
  • the reversible specific capacity and stable cycle performance show good application prospects.
  • the manganese dioxide secondary sphere is composed of a large amount of manganese dioxide nanosheets, and has a high bulk density as a negative electrode active material, which is advantageous for increasing the capacity-volume ratio of the battery.
  • FIG 3 is a graph showing electrochemical performance curves of a secondary ball of a negative active material MnO 2 synthesized according to an embodiment of the present invention.
  • the lithium ion battery negative active material provided by the present invention, a preparation method thereof and a lithium ion battery will be further described in detail below with reference to the accompanying drawings and specific embodiments.
  • Embodiments of the present invention provide a lithium ion anode active material, including manganese dioxide (MnO 2 ) secondary spheres.
  • MnO 2 manganese dioxide
  • the secondary sphere is composed of a plurality of petal MnO 2 nanosheets.
  • the MnO 2 secondary sphere has a diameter of about 1 ⁇ m to 5 ⁇ m, and the valve-shaped MnO 2 nanosheet has a thickness of about 8 nm to 10 nm.
  • the plurality of nanosheets are stacked together to form the MnO 2 secondary sphere, and the nanosheet extends from the center of the sphere to the outer surface of the secondary sphere, and a gap exists between the nanosheets, so that lithium ions can be easily penetrated from the outer surface to the second time.
  • the inside of the ball The MnO 2 secondary sphere is used as a negative electrode active material for a lithium ion battery negative-current charge and discharge cycle 100 times, and the reversible specific capacity (ie, charge specific capacity) is greater than 800 mAh/g.
  • the MnO 2 secondary sphere has good electrical conductivity and can be used alone as a negative active material for a lithium ion battery, and does not need to form a composite material with a conductive material such as graphene, conductive carbon black or carbon nanotubes.
  • Embodiments of the present invention provide a method for preparing a lithium ion negative electrode active material, which includes the following steps:
  • the solution is hydrothermally reacted in a hydrothermal kettle at a reaction temperature of 120 ° C to 160 ° C and a holding time of 0.5 h to 2 h to form a secondary sphere of MnO 2 .
  • potassium permanganate may be dissolved in water to be disposed as a potassium permanganate solution, and the potassium permanganate solution is mixed with a hydrochloric acid solution to form the solution, and the mass percentage of hydrochloric acid used is greater than 36%.
  • the solution consists only of potassium permanganate, HCl and water and does not contain other additives such as surfactants.
  • the molar ratio of potassium permanganate to HCl may be from 1:10 to 4:1.
  • the concentration of potassium permanganate in the solution is preferably from 0.01 mol/L to 1 mol/L.
  • step S2 the solution is placed in a hydrothermal reaction vessel, and the hydrothermal kettle is sealed and heated to 120 ° C to 160 ° C for hydrothermal reaction, and the incubation time is 0.5 h to 2 h at the reaction temperature.
  • the hydrothermal kettle was naturally cooled to room temperature, and the black precipitate in the hydrothermal kettle was collected, centrifuged with deionized water to remove impurity ions, and then dried in the air to obtain a MnO 2 secondary sphere.
  • the MnO 2 secondary sphere is obtained by one step synthesis by the hydrothermal reaction.
  • potassium permanganate and HCl can be redoxed to form MnO 2 having a quadratic spherical appearance.
  • the black precipitate prepared by the above method is centrifuged with deionized water to remove impurity ions, and then dried in air for XRD test, which is consistent with the standard XRD pattern of MnO 2 to prove the chemical composition of the synthesized product. It is MnO 2 .
  • SEM analysis of the above product revealed that a MnO 2 secondary sphere was formed, which consisted of a plurality of valvular nanosheets. The diameter of the secondary sphere is between 1 and 5 ⁇ m, and the thickness of the petal nanosheet is about 8 nm to 10 nm.
  • the plurality of nanosheets are stacked together to form the MnO 2 secondary sphere, and the nanosheet extends from the center of the sphere to the outer surface of the secondary sphere, and a gap exists between the nanosheets, so that lithium ions can be easily penetrated from the outer surface to the second time.
  • the inside of the ball The gap between the nanosheets is narrow (about 1 nm to 10 nm), and the nanosheets are densely packed, so that the entire sphere has a higher density, and the sphere is easy to obtain a higher bulk density, so the MnO 2 secondary sphere It is beneficial to increase the capacity to volume ratio of the battery.
  • the embodiment of the invention further provides a lithium ion battery, wherein the anode active material of the lithium ion battery is composed of the MnO 2 secondary sphere prepared by the above method, has a high first discharge specific capacity, and has stable cycle performance and capacity retention.
  • the ratio is higher, and the reversible specific capacity is greater than 800 mAh/g after 100 cycles of constant current charge and discharge.
  • the MnO 2 secondary ball is used as the negative electrode active material of the lithium ion battery to prepare the negative electrode pole piece.
  • the specific process is: mixing the MnO 2 secondary ball and the conductive agent acetylene black uniformly, and then adding the binder SBR/CMC to form a slurry. Evenly coated on copper foil, dried and then cut into negative pole pieces.
  • the mass ratio of MnO 2 , acetylene black, CMC:SBR is 75:15:5:5.
  • An EC/DMC/DEC) (1:1:1, v/v) solvent containing 1 mol/L LiPF 6 was used as an electrolyte, and lithium metal was used as a counter electrode to assemble a lithium ion battery.
  • the lithium ion battery is subjected to electrochemical cycle performance test, and the charge and discharge voltage ranges from 0.01 V to 3.0 V, and the current is 100 mA/g.
  • the first discharge specific capacity of the negative active material MnO 2 secondary sphere is about 1670 mAh/g
  • the first reversible specific capacity is as high as 1281 mAh/g
  • the reversible specific capacity of 852 mAh/g can still be obtained after 100 cycles.
  • the manganese dioxide secondary ball provided by the invention has simple preparation process and good electrical conductivity, can be directly used as a negative active material of a lithium ion battery without complexing with a conductive material, has a high reversible specific capacity, and has a circulation. The performance is stable and shows a good application prospect.
  • the manganese dioxide secondary sphere is composed of a large amount of manganese dioxide nanosheets, and has a high bulk density as a negative electrode active material, which is advantageous for increasing the capacity-volume ratio of the battery.

Abstract

A method for preparing a negative electrode active material. The method comprises the following steps: mixing potassium permanganate and hydrogen chloride in water to form a solution; and performing hydrothermal reaction of the solution in a hydrothermal kettle to generate manganese dioxide secondary balls, the solution in the hydrothermal kettle consisting of potassium permanganate, hydrogen chloride and water, the reaction temperature being 120ºC to 160ºC, and the heat preservation time being 0.5 hour to 2 hours. The present invention also provides a lithium-ion battery. The negative electrode active material of the lithium-ion battery consists of the manganese dioxide secondary balls.

Description

负极活性材料及其制备方法以及锂离子电池Anode active material, preparation method thereof and lithium ion battery 技术领域Technical field
本发明涉及一种锂离子电池负极活性材料及其制备方法以及锂离子电池。The invention relates to a lithium ion battery anode active material, a preparation method thereof and a lithium ion battery.
背景技术Background technique
锂离子电池商业化的负极材料大多采用石墨，但是石墨材料的理论储锂比容量只有372mAh/g。为满足高容量锂离子电池的需求，研究开发新型的高比容量锂离子电池负极材料替代目前商业化应用的石墨负极材料显得非常迫切和必要。Most of the negative electrode materials commercialized by lithium ion batteries use graphite, but the theoretical lithium storage capacity of graphite materials is only 372 mAh/g. In order to meet the demand of high-capacity lithium-ion batteries, it is very urgent and necessary to research and develop a new high-capacity lithium-ion battery anode material to replace the graphite anode material currently used in commercial applications.
自从2000年Poizot等人首次报道过渡金属氧化物(TMOs, transition metal oxides)作为锂离子电池负极材料以来，过渡金属氧化物以及其他过渡金属化合物（TMX）作为锂离子电池负极材料颇受关注。过渡金属的氧化物，如Fe、Ni、Co、Cu等，一般具有类似的电化学行为。其脱嵌锂机理一般是：嵌锂时，Li嵌入到过渡金属氧化物中，通过置换反应生成金属纳米颗粒，并均匀包埋在生成的Li2O基质中；脱锂时，又可逆生成过渡金属氧化物和锂。Since Poizot et al. first reported transition metal oxides (TMOs) as anode materials for lithium-ion batteries in 2000, transition metal oxides and other transition metal compounds (TMX) have attracted much attention as anode materials for lithium-ion batteries. Oxides of transition metals, such as Fe, Ni, Co, Cu, etc., generally have similar electrochemical behavior. The mechanism of lithium deintercalation is generally: when lithium is intercalated, Li is embedded in the transition metal oxide, and metal nanoparticles are formed by displacement reaction and uniformly embedded in the generated Li 2 O matrix; when delithiation, reversible transition is generated. Metal oxides and lithium.
在这些过渡金属氧化物中，金属锰的氧化物，如MnO、Mn3O4、Mn2O3、MnO2等，广泛应用于各类电化学储能设备而引起广泛的兴趣。锰的氧化物具有众多的结构，其电化学行为强烈依赖于氧化态、纳米结构和形态。根据理论计算，MnO、Mn3O4、Mn2O3、MnO2的理论储锂比容量分别为755、936、1018、1232mAh/g。因此MnO2的比容量最高。传统上，MnO2在电池领域中作为一次锂电池的正极材料广泛使用，由于其较低的可逆容量和较差的循环稳定性无法应用于二次锂离子电池。Among these transition metal oxides, metal manganese oxides such as MnO, Mn 3 O 4 , Mn 2 O 3 , MnO 2 and the like are widely used in various types of electrochemical energy storage devices and have attracted wide interest. Manganese oxides have numerous structures, and their electrochemical behavior is strongly dependent on oxidation states, nanostructures, and morphology. According to theoretical calculations, the theoretical lithium storage capacities of MnO, Mn 3 O 4 , Mn 2 O 3 , and MnO 2 are 755, 936, 1018, and 1232 mAh/g, respectively. Therefore, the specific capacity of MnO 2 is the highest. Conventionally, MnO 2 has been widely used as a positive electrode material for primary lithium batteries in the field of batteries, and cannot be applied to secondary lithium ion batteries due to its low reversible capacity and poor cycle stability.
近年来，由于MnO2具有较高的理论比容量，以及丰富的自然资源，对MnO2作为锂离子电池负极材料的研究有增多的趋势，然而，MnO2电化学性能远远无法令人满意，首次可逆比容量较低，更无法令人接受的是循环性能极差，多次循环后容量衰减迅速。甚至有研究者怀疑MnO2是否具有电化学活性，能否应用于二次锂离子电池。In recent years, MnO 2 has a high theoretical specific capacity, and is rich in natural resources, there is a growing trend in the study as a lithium-ion battery anode material of MnO 2, however, is far MnO 2 electrochemical performance not satisfactory, The first reversible specific capacity is low, and it is even more unacceptable that the cycle performance is extremely poor, and the capacity decays rapidly after repeated cycles. Even researchers have doubted whether MnO 2 is electrochemically active and can be applied to secondary lithium-ion batteries.
发明内容Summary of the invention
有鉴于此，确有必要提供一种锂离子电池负极活性材料及其制备方法以及锂离子电池，该锂离子电池负极活性材料具有较高的首次可逆比容量和优异的循环性能，可用于二次锂离子电池。In view of this, it is indeed necessary to provide a lithium ion battery anode active material and a preparation method thereof, and a lithium ion battery, the lithium ion battery anode active material has a high first reversible specific capacity and excellent cycle performance, and can be used for secondary Lithium Ion Battery.
一种负极活性材料的制备方法，其包括以下步骤：将高锰酸钾与氯化氢在水中混合形成溶液；以及将该溶液在水热釜中进行水热反应，该水热釜中的溶液由高锰酸钾、氯化氢及水组成，反应温度为120℃~160℃，保温时间为0.5小时~2小时，生二氧化锰二次球，该二氧化锰二次球由多个二氧化锰纳米片组成。A method for preparing a negative electrode active material, comprising the steps of: mixing potassium permanganate with hydrogen chloride in water to form a solution; and hydrothermally reacting the solution in a hydrothermal kettle, wherein the solution in the hydrothermal kettle is high Potassium manganate, hydrogen chloride and water, the reaction temperature is 120 ° C ~ 160 ° C, the holding time is 0.5 hour ~ 2 hours, the manganese dioxide secondary ball, the manganese dioxide secondary ball from the plurality of manganese dioxide nanosheets composition.
一种负极活性材料，由二氧化锰二次球组成。An anode active material consisting of a manganese dioxide secondary sphere.
一种锂离子电池，该锂离子电池的负极活性材料由二氧化锰二次球组成。A lithium ion battery, the anode active material of the lithium ion battery being composed of a manganese dioxide secondary sphere.
相较于现有技术，本发明提供的二氧化锰二次球制备工艺简单，并且具有较好的导电性能，能够无需与导电材料复合即可直接作为锂离子电池负极活性材料应用，具有较高的可逆比容量，且循环性能稳定，显示出良好的应用前景。该二氧化锰二次球由大量二氧化锰纳米片堆积组成，作为负极活性材料具有较高的堆积密度，有利于提高电池的容量体积比。Compared with the prior art, the manganese dioxide secondary ball provided by the invention has simple preparation process and good electrical conductivity, and can be directly used as a negative active material of a lithium ion battery without being combined with a conductive material, and has a higher performance. The reversible specific capacity and stable cycle performance show good application prospects. The manganese dioxide secondary sphere is composed of a large amount of manganese dioxide nanosheets, and has a high bulk density as a negative electrode active material, which is advantageous for increasing the capacity-volume ratio of the battery.
附图说明DRAWINGS
图1为本发明实施例合成的负极活性材料MnO2二次球的XRD图。1 is an XRD chart of a secondary sphere of a negative active material MnO 2 synthesized according to an embodiment of the present invention.
图2为本发明实施例合成的负极活性材料MnO2二次球的SEM图。2 is an SEM image of a secondary sphere of a negative active material MnO 2 synthesized in accordance with an embodiment of the present invention.
图3为本发明实施例合成的负极活性材料MnO2二次球的电化学性能曲线。3 is a graph showing electrochemical performance curves of a secondary ball of a negative active material MnO 2 synthesized according to an embodiment of the present invention.
图4为对比例1合成的MnO2纳米棒的SEM图。4 is an SEM image of the MnO 2 nanorods synthesized in Comparative Example 1.
图5为对比例4合成的MnO2纳米管的SEM图。5 is an SEM image of the MnO 2 nanotubes synthesized in Comparative Example 4.
具体实施方式detailed description
下面将结合附图及具体实施例对本发明提供的锂离子电池负极活性材料及其制备方法以及锂离子电池作进一步的详细说明。The lithium ion battery negative active material provided by the present invention, a preparation method thereof and a lithium ion battery will be further described in detail below with reference to the accompanying drawings and specific embodiments.
本发明实施例提供一种锂离子负极活性材料，包括二氧化锰(MnO2)二次球。Embodiments of the present invention provide a lithium ion anode active material, including manganese dioxide (MnO 2 ) secondary spheres.
具体地，该二次球由大量瓣状MnO2纳米片组成。该MnO2二次球直径约为1μm~5μm，瓣状MnO2纳米片厚度大约为8nm~10nm左右。该大量纳米片相互堆积共同组正该MnO2二次球，纳米片从球心延伸至二次球外表面，纳米片之间存在间隙，从而可以使锂离子容易地从外表面深入到二次球内部。该MnO2二次球作为锂离子电池负极活性材料恒流充放电循环100次后可逆比容量（即充电比容量）大于800mAh/g。Specifically, the secondary sphere is composed of a plurality of petal MnO 2 nanosheets. The MnO 2 secondary sphere has a diameter of about 1 μm to 5 μm, and the valve-shaped MnO 2 nanosheet has a thickness of about 8 nm to 10 nm. The plurality of nanosheets are stacked together to form the MnO 2 secondary sphere, and the nanosheet extends from the center of the sphere to the outer surface of the secondary sphere, and a gap exists between the nanosheets, so that lithium ions can be easily penetrated from the outer surface to the second time. The inside of the ball. The MnO 2 secondary sphere is used as a negative electrode active material for a lithium ion battery negative-current charge and discharge cycle 100 times, and the reversible specific capacity (ie, charge specific capacity) is greater than 800 mAh/g.
该MnO2二次球具有良好的导电性，可以单独作为锂离子电池负极活性材料，无需与导电材料，如石墨烯、导电炭黑或碳纳米管等形成复合材料。The MnO 2 secondary sphere has good electrical conductivity and can be used alone as a negative active material for a lithium ion battery, and does not need to form a composite material with a conductive material such as graphene, conductive carbon black or carbon nanotubes.
本发明实施例提供一种锂离子负极活性材料的制备方法，其包括以下步骤：Embodiments of the present invention provide a method for preparing a lithium ion negative electrode active material, which includes the following steps:
S1，将高锰酸钾(KMnO4)与氯化氢(HCl)在水中混合形成溶液；以及S1, mixing potassium permanganate (KMnO 4 ) with hydrogen chloride (HCl) in water to form a solution;
S2，将该溶液在水热釜中进行水热反应，反应温度为120℃~160℃，保温时间为0.5h~2h，生成MnO2二次球。S2, the solution is hydrothermally reacted in a hydrothermal kettle at a reaction temperature of 120 ° C to 160 ° C and a holding time of 0.5 h to 2 h to form a secondary sphere of MnO 2 .
具体地，在该步骤S1中，可将高锰酸钾溶解于水中配置成高锰酸钾溶液，再将该高锰酸钾溶液与盐酸溶液混合形成所述溶液，所用盐酸的质量百分比浓度大于36%。该溶液仅由高锰酸钾、HCl及水组成，不含表面活性剂等其他添加剂。在该溶液中，高锰酸钾和HCl的摩尔比可以为1:10~4:1。该溶液中高锰酸钾的浓度优选为0.01 mol/L~1mol/L。Specifically, in this step S1, potassium permanganate may be dissolved in water to be disposed as a potassium permanganate solution, and the potassium permanganate solution is mixed with a hydrochloric acid solution to form the solution, and the mass percentage of hydrochloric acid used is greater than 36%. The solution consists only of potassium permanganate, HCl and water and does not contain other additives such as surfactants. In this solution, the molar ratio of potassium permanganate to HCl may be from 1:10 to 4:1. The concentration of potassium permanganate in the solution is preferably from 0.01 mol/L to 1 mol/L.
在该步骤S2中，将该溶液放入水热反应釜中，将水热釜密封并加热至120℃~160℃进行水热反应，在该反应温度下保温时间为0.5h~2h。In this step S2, the solution is placed in a hydrothermal reaction vessel, and the hydrothermal kettle is sealed and heated to 120 ° C to 160 ° C for hydrothermal reaction, and the incubation time is 0.5 h to 2 h at the reaction temperature.
反应完毕后水热釜自然冷却至室温，收集水热釜中的黑色沉淀，用去离子水离心洗涤以去除杂质离子，然后在空气中干燥，得到MnO2二次球。该MnO2二次球为通过该水热反应一步合成得到。After the completion of the reaction, the hydrothermal kettle was naturally cooled to room temperature, and the black precipitate in the hydrothermal kettle was collected, centrifuged with deionized water to remove impurity ions, and then dried in the air to obtain a MnO 2 secondary sphere. The MnO 2 secondary sphere is obtained by one step synthesis by the hydrothermal reaction.
在此水热反应中，通过控制溶液组分、反应温度以及保温时间，可以使高锰酸钾与HCl发生氧化还原反应生成具有二次球形貌的MnO2。In this hydrothermal reaction, by controlling the composition of the solution, the reaction temperature, and the holding time, potassium permanganate and HCl can be redoxed to form MnO 2 having a quadratic spherical appearance.
请参阅图1，对上述方法制备得到的黑色沉淀用去离子水离心洗涤以去除杂质离子，然后在空气中干燥后进行XRD测试，与MnO2的标准XRD图相符合，证明合成产物化学组分为MnO2。请参阅图2，对上述产物进行SEM分析，可以看到形成了MnO2二次球，该二次球由大量瓣状纳米片组成。该二次球的直径在1~5μm之间，瓣状纳米片厚度大约为8nm~10nm左右。该大量纳米片相互堆积共同组正该MnO2二次球，纳米片从球心延伸至二次球外表面，纳米片之间存在间隙，从而可以使锂离子容易地从外表面深入到二次球内部。该纳米片之间的间隙较窄（约1nm~10nm），纳米片堆积较为紧密，使二次球整体具有较高的密度，而球体容易获得较高的堆积密度，因此该MnO2二次球有利于提高电池的容量体积比。Referring to Figure 1, the black precipitate prepared by the above method is centrifuged with deionized water to remove impurity ions, and then dried in air for XRD test, which is consistent with the standard XRD pattern of MnO 2 to prove the chemical composition of the synthesized product. It is MnO 2 . Referring to FIG. 2, SEM analysis of the above product revealed that a MnO 2 secondary sphere was formed, which consisted of a plurality of valvular nanosheets. The diameter of the secondary sphere is between 1 and 5 μm, and the thickness of the petal nanosheet is about 8 nm to 10 nm. The plurality of nanosheets are stacked together to form the MnO 2 secondary sphere, and the nanosheet extends from the center of the sphere to the outer surface of the secondary sphere, and a gap exists between the nanosheets, so that lithium ions can be easily penetrated from the outer surface to the second time. The inside of the ball. The gap between the nanosheets is narrow (about 1 nm to 10 nm), and the nanosheets are densely packed, so that the entire sphere has a higher density, and the sphere is easy to obtain a higher bulk density, so the MnO 2 secondary sphere It is beneficial to increase the capacity to volume ratio of the battery.
本发明实施例进一步提供一种锂离子电池，该锂离子电池的负极活性材料由通过上述方法制备得到的MnO2二次球组成，具有较高的首次放电比容量，且循环性能稳定，容量保持率较高，恒流充放电循环100次后可逆比容量大于800mAh/g。The embodiment of the invention further provides a lithium ion battery, wherein the anode active material of the lithium ion battery is composed of the MnO 2 secondary sphere prepared by the above method, has a high first discharge specific capacity, and has stable cycle performance and capacity retention. The ratio is higher, and the reversible specific capacity is greater than 800 mAh/g after 100 cycles of constant current charge and discharge.
实施例1Example 1
将1毫摩尔(mmol) KMnO4和4 mmol HCl（浓度为36%的浓盐酸）溶解于45 ml去离子水形成溶液。然后将该溶液转移至65 ml容积的水热釜内胆中。密封水热釜加热至140℃，保温2小时。反应完毕后水热釜自然冷却至室温，收集釜中的黑色沉淀，用去离子水离心洗涤以除去杂质离子，然后在空气中干燥，得到MnO2二次球。1 mmol (mmol) of KMnO 4 and 4 mmol of HCl (concentration of 36% concentrated hydrochloric acid) were dissolved in 45 ml of deionized water to form a solution. The solution was then transferred to a 65 ml volume of hydrothermal kettle liner. The sealed water hot kettle was heated to 140 ° C and kept for 2 hours. After completion of the reaction, the hydrothermal kettle was naturally cooled to room temperature, and a black precipitate in the kettle was collected, centrifuged with deionized water to remove impurity ions, and then dried in the air to obtain a MnO 2 secondary sphere.
将MnO2二次球作为锂离子电池负极活性材料制作负电极极片，具体过程是：将MnO2二次球及导电剂乙炔黑混合均匀，然后加入粘结剂SBR/CMC制成浆料，均匀涂于铜箔上，烘干后剪切成负极极片。MnO2、乙炔黑、CMC：SBR的质量比为75:15:5:5。以含1mol/L LiPF6的EC/DMC/DEC) (1:1:1，v/v)溶剂为电解液，金属锂为对电极，组装成锂离子电池。The MnO 2 secondary ball is used as the negative electrode active material of the lithium ion battery to prepare the negative electrode pole piece. The specific process is: mixing the MnO 2 secondary ball and the conductive agent acetylene black uniformly, and then adding the binder SBR/CMC to form a slurry. Evenly coated on copper foil, dried and then cut into negative pole pieces. The mass ratio of MnO 2 , acetylene black, CMC:SBR is 75:15:5:5. An EC/DMC/DEC) (1:1:1, v/v) solvent containing 1 mol/L LiPF 6 was used as an electrolyte, and lithium metal was used as a counter electrode to assemble a lithium ion battery.
请参阅图3，将该锂离子电池进行电化学循环性能测试，充放电电压范围为0.01V~3.0V，电流为100mA/g。从图3可以看到，负极活性材料MnO2二次球首次放电比容量约为1670mAh/g，首次可逆比容量高达1281mAh/g，100次循环后仍可具有852mAh/g的可逆比容量。Referring to FIG. 3, the lithium ion battery is subjected to electrochemical cycle performance test, and the charge and discharge voltage ranges from 0.01 V to 3.0 V, and the current is 100 mA/g. It can be seen from Fig. 3 that the first discharge specific capacity of the negative active material MnO 2 secondary sphere is about 1670 mAh/g, the first reversible specific capacity is as high as 1281 mAh/g, and the reversible specific capacity of 852 mAh/g can still be obtained after 100 cycles.
实施例2Example 2
将1 mmol KMnO4和10 mmol HCl（浓度为36%的浓盐酸）溶解于45 ml去离子水形成溶液。然后将溶液转移至65 ml容积的水热釜内胆中。密封水热釜加热至120 ℃，保温2小时。反应完毕后水热釜自然冷却至室温，收集釜中的黑色沉淀，用去离子水离心洗涤以除去杂质离子，然后在空气中干燥，得到MnO2二次球。1 mmol of KMnO 4 and 10 mmol of HCl (concentration of 36% concentrated hydrochloric acid) were dissolved in 45 ml of deionized water to form a solution. The solution was then transferred to a 65 ml volume of hydrothermal kettle liner. The sealed water hot kettle was heated to 120 ° C and kept for 2 hours. After completion of the reaction, the hydrothermal kettle was naturally cooled to room temperature, and a black precipitate in the kettle was collected, centrifuged with deionized water to remove impurity ions, and then dried in the air to obtain a MnO 2 secondary sphere.
实施例3：Example 3:
将4 mmol KMnO4和1 mmol HCl（浓度为36%的浓盐酸）溶解于45 mL去离子水形成溶液。然后将该混合液转移至65 ml容积的水热釜内胆中。密封水热釜加热至160 ℃，保温0.5小时。反应完毕后水热釜自然冷却至室温，收集釜中的黑色沉淀，用去离子水离心洗涤以除去杂质离子，然后在空气中干燥，得到MnO2二次球。4 mmol of KMnO 4 and 1 mmol of HCl (concentration of 36% concentrated hydrochloric acid) were dissolved in 45 mL of deionized water to form a solution. The mixture was then transferred to a 65 ml volume of hydrothermal kettle liner. The sealed water hot kettle was heated to 160 ° C and held for 0.5 hours. After completion of the reaction, the hydrothermal kettle was naturally cooled to room temperature, and a black precipitate in the kettle was collected, centrifuged with deionized water to remove impurity ions, and then dried in the air to obtain a MnO 2 secondary sphere.
实施例4：Example 4:
将1 mmol KMnO4和4 mmol HCl（浓度为36%的浓盐酸）溶解于45 ml去离子水形成溶液。然后将该混合液转移至65 ml容积的水热釜内胆中。密封水热釜加热至140℃，保温0.5小时。反应完毕后水热釜自然冷却至室温，收集釜中的黑色沉淀，用去离子水离心洗涤以除去杂质离子，然后在空气中干燥，得到MnO2二次球。1 mmol of KMnO 4 and 4 mmol of HCl (concentration of 36% concentrated hydrochloric acid) were dissolved in 45 ml of deionized water to form a solution. The mixture was then transferred to a 65 ml volume of hydrothermal kettle liner. The sealed water hot kettle was heated to 140 ° C and held for 0.5 hours. After completion of the reaction, the hydrothermal kettle was naturally cooled to room temperature, and a black precipitate in the kettle was collected, centrifuged with deionized water to remove impurity ions, and then dried in the air to obtain a MnO 2 secondary sphere.
实施例5：Example 5:
将1 mmol KMnO4和4 mmol HCl（浓度为36%的浓盐酸）溶解于45 ml去离子水形成溶液。然后将该混合液转移至65 ml容积的水热釜内胆中。密封水热釜加热至140 ℃，保温1小时。反应完毕后水热釜自然冷却至室温，收集釜中的黑色沉淀，用去离子水离心洗涤以除去杂质离子，然后在空气中干燥，得到MnO2二次球。1 mmol of KMnO 4 and 4 mmol of HCl (concentration of 36% concentrated hydrochloric acid) were dissolved in 45 ml of deionized water to form a solution. The mixture was then transferred to a 65 ml volume of hydrothermal kettle liner. The sealed water hot kettle was heated to 140 ° C and kept for 1 hour. After completion of the reaction, the hydrothermal kettle was naturally cooled to room temperature, and a black precipitate in the kettle was collected, centrifuged with deionized water to remove impurity ions, and then dried in the air to obtain a MnO 2 secondary sphere.
实施例6：Example 6
将1 mmol KMnO4和4 mmol HCl（浓度为36%的浓盐酸）溶解于45 ml去离子水形成溶液。然后将该混合液转移至65 ml容积的水热釜内胆中。密封水热釜加热至120 ℃，保温0.5小时。反应完毕后水热釜自然冷却至室温，收集釜中的黑色沉淀，用去离子水离心洗涤以除去杂质离子，然后在空气中干燥，得到MnO2二次球。1 mmol of KMnO 4 and 4 mmol of HCl (concentration of 36% concentrated hydrochloric acid) were dissolved in 45 ml of deionized water to form a solution. The mixture was then transferred to a 65 ml volume of hydrothermal kettle liner. The sealed water hot kettle was heated to 120 ° C and held for 0.5 hours. After completion of the reaction, the hydrothermal kettle was naturally cooled to room temperature, and a black precipitate in the kettle was collected, centrifuged with deionized water to remove impurity ions, and then dried in the air to obtain a MnO 2 secondary sphere.
对比例1Comparative example 1
将1毫摩尔(mmol) KMnO4和4 mmol HCl（浓度为36%的浓盐酸）溶解于45 ml去离子水形成溶液。然后将该溶液转移至65 ml容积的水热釜内胆中。密封水热釜加热至140℃，保温4小时。反应完毕后水热釜自然冷却至室温，收集釜中的黑色沉淀，用去离子水离心洗涤以除去杂质离子，然后在空气中干燥，得到MnO2产物。请参阅图4，对上述产物进行SEM分析，可以看到形成了MnO2纳米棒，该MnO2纳米棒长度小于10μm，直径约为50nm~200nm，优选为100nm左右。1 mmol (mmol) of KMnO 4 and 4 mmol of HCl (concentration of 36% concentrated hydrochloric acid) were dissolved in 45 ml of deionized water to form a solution. The solution was then transferred to a 65 ml volume of hydrothermal kettle liner. The sealed water hot kettle was heated to 140 ° C and kept for 4 hours. After completion of the reaction, the hydrothermal kettle was naturally cooled to room temperature, and a black precipitate in the kettle was collected, washed with deionized water to remove impurity ions, and then dried in air to obtain a MnO 2 product. Referring to FIG. 4, SEM analysis of the above product revealed that MnO 2 nanorods were formed, the MnO 2 nanorods having a length of less than 10 μm and a diameter of about 50 nm to 200 nm, preferably about 100 nm.
对比例2Comparative example 2
将1 mmol KMnO4和10 mmol HCl（浓度为36%的浓盐酸）溶解于45 ml去离子水形成溶液。然后将溶液转移至65 ml容积的水热釜内胆中。密封水热釜加热至120 ℃，保温3小时。反应完毕后水热釜自然冷却至室温，收集釜中的黑色沉淀，用去离子水离心洗涤以除去杂质离子，然后在空气中干燥，得到MnO2纳米棒。1 mmol of KMnO 4 and 10 mmol of HCl (concentration of 36% concentrated hydrochloric acid) were dissolved in 45 ml of deionized water to form a solution. The solution was then transferred to a 65 ml volume of hydrothermal kettle liner. The sealed water hot kettle was heated to 120 ° C and kept for 3 hours. After completion of the reaction, the hydrothermal kettle was naturally cooled to room temperature, and the black precipitate in the kettle was collected, centrifuged with deionized water to remove impurity ions, and then dried in the air to obtain MnO 2 nanorods.
对比例3Comparative example 3
将4 mmol KMnO4和1 mmol HCl（浓度为36%的浓盐酸）溶解于45 mL去离子水形成溶液。然后将该混合液转移至65 ml容积的水热釜内胆中。密封水热釜加热至160 ℃，保温3小时。反应完毕后水热釜自然冷却至室温，收集釜中的黑色沉淀，用去离子水离心洗涤以除去杂质离子，然后在空气中干燥，得到MnO2纳米棒。4 mmol of KMnO 4 and 1 mmol of HCl (concentration of 36% concentrated hydrochloric acid) were dissolved in 45 mL of deionized water to form a solution. The mixture was then transferred to a 65 ml volume of hydrothermal kettle liner. The sealed water hot kettle was heated to 160 ° C and kept for 3 hours. After completion of the reaction, the hydrothermal kettle was naturally cooled to room temperature, and the black precipitate in the kettle was collected, centrifuged with deionized water to remove impurity ions, and then dried in the air to obtain MnO 2 nanorods.
对比例4Comparative example 4
将1 mmol KMnO4和4 mmol HCl（浓度为36%的浓盐酸）溶解于45 ml去离子水形成溶液。然后将该混合液转移至65 ml容积的水热釜内胆中。密封水热釜加热至140℃，保温10小时。反应完毕后水热釜自然冷却至室温，收集釜中的黑色沉淀，用去离子水离心洗涤以除去杂质离子，然后在空气中干燥，得到MnO2纳米棒。1 mmol of KMnO 4 and 4 mmol of HCl (concentration of 36% concentrated hydrochloric acid) were dissolved in 45 ml of deionized water to form a solution. The mixture was then transferred to a 65 ml volume of hydrothermal kettle liner. The sealed water hot kettle was heated to 140 ° C and kept for 10 hours. After completion of the reaction, the hydrothermal kettle was naturally cooled to room temperature, and the black precipitate in the kettle was collected, centrifuged with deionized water to remove impurity ions, and then dried in the air to obtain MnO 2 nanorods.
对比例5Comparative example 5
将1 mmol KMnO4和4 mmol HCl（浓度为36%的浓盐酸）溶解于45 ml去离子水形成溶液，加入4 mg表面活性剂聚乙烯吡咯烷酮，形成混合液。然后将该混合液转移至65 ml容积的水热釜内胆中。密封水热釜加热至140℃，保温2小时。反应完毕后水热釜自然冷却至室温，收集釜中的黑色沉淀，用去离子水离心洗涤以除去杂质离子，然后在空气中干燥，得到MnO2产物。请参阅图5，对上述产物进行SEM分析，可以看到形成了MnO2纳米管。1 mmol of KMnO 4 and 4 mmol of HCl (concentration of 36% concentrated hydrochloric acid) were dissolved in 45 ml of deionized water to form a solution, and 4 mg of surfactant polyvinylpyrrolidone was added to form a mixed solution. The mixture was then transferred to a 65 ml volume of hydrothermal kettle liner. The sealed water hot kettle was heated to 140 ° C and kept for 2 hours. After completion of the reaction, the hydrothermal kettle was naturally cooled to room temperature, and a black precipitate in the kettle was collected, washed with deionized water to remove impurity ions, and then dried in air to obtain a MnO 2 product. Referring to Figure 5, SEM analysis of the above products revealed that MnO 2 nanotubes were formed.
从上述对比例1~4可以看到，该二氧化锰产物的形貌与保温时间存在较大关系，当保温时间较长，如3小时~10小时，无法得到所述MnO2二次球。从上述对比例5可以看到，当该反应溶液中含有其他组分，如表面活性剂时也会影响该产物的形貌，而无法得到所述MnO2二次球。It can be seen from the above Comparative Examples 1 to 4 that the morphology of the manganese dioxide product has a great relationship with the holding time. When the holding time is long, such as 3 hours to 10 hours, the MnO 2 secondary ball cannot be obtained. It can be seen from the above Comparative Example 5 that when the reaction solution contains other components such as a surfactant, the morphology of the product is also affected, and the MnO 2 secondary sphere cannot be obtained.
本发明提供的二氧化锰二次球制备工艺简单，并且具有较好的导电性能，能够无需与导电材料复合即可直接作为锂离子电池负极活性材料应用，具有较高的可逆比容量，且循环性能稳定，显示出良好的应用前景。该二氧化锰二次球由大量二氧化锰纳米片堆积组成，作为负极活性材料具有较高的堆积密度，有利于提高电池的容量体积比。The manganese dioxide secondary ball provided by the invention has simple preparation process and good electrical conductivity, can be directly used as a negative active material of a lithium ion battery without complexing with a conductive material, has a high reversible specific capacity, and has a circulation. The performance is stable and shows a good application prospect. The manganese dioxide secondary sphere is composed of a large amount of manganese dioxide nanosheets, and has a high bulk density as a negative electrode active material, which is advantageous for increasing the capacity-volume ratio of the battery.
另外，本领域技术人员还可在本发明精神内做其他变化，当然，这些依据本发明精神所做的变化，都应包含在本发明所要求保护的范围之内。In addition, those skilled in the art can make other changes in the spirit of the present invention. Of course, the changes made in accordance with the spirit of the present invention should be included in the scope of the present invention.

Claims (10)

  1. 一种负极活性材料的制备方法，其包括以下步骤：A method for preparing a negative active material, comprising the steps of:
    将高锰酸钾与氯化氢在水中混合形成溶液；以及Mixing potassium permanganate with hydrogen chloride in water to form a solution;
    将该溶液在水热釜中进行水热反应，该水热釜中的溶液由高锰酸钾、氯化氢及水组成，反应温度为120℃~160℃，保温时间为0.5小时~2小时，生成二氧化锰二次球，该二氧化锰二次球由多个二氧化锰纳米片组成。The solution is hydrothermally reacted in a hydrothermal kettle. The solution in the hydrothermal kettle is composed of potassium permanganate, hydrogen chloride and water. The reaction temperature is 120 ° C to 160 ° C, and the holding time is 0.5 hours to 2 hours. A manganese dioxide secondary sphere composed of a plurality of manganese dioxide nanosheets.
  2. 如权利要求1所述的负极活性材料的制备方法，其特征在于，该高锰酸钾和氯化氢的摩尔比为1:10~4:1。The method for producing a negative electrode active material according to claim 1, wherein the molar ratio of the potassium permanganate to hydrogen chloride is from 1:10 to 4:1.
  3. 如权利要求1所述的负极活性材料的制备方法，其特征在于，该溶液中高锰酸钾的浓度为0.01 mol/L~1mol/L。The method for producing a negative electrode active material according to claim 1, wherein the concentration of potassium permanganate in the solution is from 0.01 mol/L to 1 mol/L.
  4. 一种负极活性材料，其特征在于，由权利要求1所述的负极活性材料的制备方法得到的二氧化锰二次球组成。A negative electrode active material comprising the manganese dioxide secondary ball obtained by the method for producing a negative electrode active material according to claim 1.
  5. 如权利要求4所述的负极活性材料，其特征在于，该二氧化锰二次球直径为1μm~5μm。The negative electrode active material according to claim 4, wherein the manganese dioxide secondary ball has a diameter of from 1 μm to 5 μm.
  6. 如权利要求4所述的负极活性材料，其特征在于，该二氧化锰纳米片厚度为8nm~10nm，二氧化锰纳米片之间存在间隙。The negative active material according to claim 4, wherein the manganese dioxide nanosheet has a thickness of 8 nm to 10 nm, and a gap exists between the manganese dioxide nanosheets.
  7. 一种锂离子电池，其特征在于，该锂离子电池的负极活性材料由权利要求1所述的负极活性材料的制备方法得到的二氧化锰二次球组成。A lithium ion battery characterized in that the negative electrode active material of the lithium ion battery is composed of the manganese dioxide secondary ball obtained by the method for producing the negative electrode active material according to claim 1.
  8. 如权利要求7所述的锂离子电池，其特征在于，该二氧化锰二次球直径为1μm~5μm。The lithium ion battery according to claim 7, wherein the manganese dioxide secondary sphere has a diameter of from 1 μm to 5 μm.
  9. 如权利要求7所述的锂离子电池，其特征在于，该二氧化锰纳米片厚度为8nm~10nm，二氧化锰纳米片之间存在间隙。The lithium ion battery according to claim 7, wherein the manganese dioxide nanosheet has a thickness of 8 nm to 10 nm, and a gap exists between the manganese dioxide nanosheets.
  10. 如权利要求7所述的锂离子电池，其特征在于，该锂离子电池恒流充放电循环100次后可逆比容量大于800mAh/g。The lithium ion battery according to claim 7, wherein the lithium ion battery has a reversible specific capacity of more than 800 mAh/g after 100 cycles of constant current charge and discharge.
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