CN109279663B - Borate sodium-ion battery negative electrode material and preparation and application thereof - Google Patents

Borate sodium-ion battery negative electrode material and preparation and application thereof Download PDF

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CN109279663B
CN109279663B CN201811331109.8A CN201811331109A CN109279663B CN 109279663 B CN109279663 B CN 109279663B CN 201811331109 A CN201811331109 A CN 201811331109A CN 109279663 B CN109279663 B CN 109279663B
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ion battery
cobalt
nickel
borate
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CN109279663A (en
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王保峰
许贝贝
马潇
嵇颖婕
平秋实
陈晗
邰子阳
殷玉森
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Shanghai University of Electric Power
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

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  • Inorganic Chemistry (AREA)
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  • Electrochemistry (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a borate sodium ion battery cathode material and preparation and application thereof, wherein the preparation of the material comprises the following steps: uniformly mixing a nickel source, a cobalt source and a boron source in a molar ratio of 2:1: 2-3, sintering and preserving heat in an oxidizing atmosphere, and cooling to obtain a target product CoNi2(BO3)2. Compared with the prior art, the CoNi of the invention2(BO3)2The material has wide raw material source, low cost, good safety performance and environmental protection, the preparation method has the characteristics of simple process flow, low equipment requirement, high product purity and the like, and the prepared CoNi2(BO3)2The material shows excellent electrochemical performance.

Description

Borate sodium-ion battery negative electrode material and preparation and application thereof
Technical Field
The invention belongs to the technical field of negative electrode materials of sodium-ion batteries, and relates to a borate type negative electrode material of a sodium-ion battery, and preparation and application thereof.
Background
The ever-increasing availability of renewable energy sources (wind, solar, tidal, etc.) has prompted researchers to continually explore inexpensive, efficient energy storage systems. Due to the characteristics of rich sodium resources, low cost and the like, the sodium-ion battery technology has certain attraction to large-scale electric energy storage and conversion, and can be used as one of the replacement choices of lithium ion batteries. Because the radius of sodium ions is far larger than that of lithium ions, the sodium storage performance of the traditional lithium ion battery cathode material is poor. Therefore, research and exploration of negative electrode materials with high specific capacity, long cycle life and high rate become the key for developing sodium ion batteries.
Among the currently known negative sodium storage materials, the graphite material is difficult to perform the deintercalation reaction in the graphite layer due to the large radius of sodium ions, and is not suitable for the negative material of the sodium ion battery. The hard carbon material is also reported to be applied to the negative electrode material of the sodium-ion battery, and the result shows that the hard carbon material has better sodium storage performance and the specific capacity can reach 200-300 mAh.g-1(Advanced Functional Materials, 2011, 21(20): 3859-. The metal and alloy negative electrode material is concerned by people because of high specific capacity, the Yanghuoxi project group adopts nano and gradient structure design, the SiC-Sb-Cu-C core-shell structure material is prepared by adopting a ball milling method, the core is made of SiC material, a layer of Sb/Cu material is prepared on the surface of the SiC core to improve the electric conductivity, and finally, a carbon coating layer is added on the surface of the outer core. The prepared core-shell material shows excellent cycling stability, and the specific capacity of the core-shell material after 100 cycles of cycling keeps 595mAh g-1(Electrochimica Acta, 2013, 87, 41-45). However, such materials have the defects of low first efficiency, large volume expansion rate, undesirable cycle life and the like in the charge-discharge cycle process.
When the polyanionic compound borate is used as the negative electrode material of the sodium-ion battery, the polyanionic compound borate has the advantages of high theoretical specific capacity, abundant reserves, environmental friendliness, wide resource distribution and the like. Yang et al adopt a hydrothermal method to prepare Zn3B2O6And as a negative electrode material of a sodium ion battery, research results show that the specific capacity of the composite material after 100 cycles in the sodium ion battery reaches 283.7mAh g-1And exhibits excellent rate capability (Bulletin of the Chemical Society of Japan, 2018.). With the continuous and deep exploration of sodium ion battery energy storage, researchers are eagerly developing novel materials with excellent electrochemical properties such as high specific capacity and excellent rate performance and simple preparation method to meet the requirement of development of sodium ion battery energy storage.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a borate sodium-ion battery negative electrode material and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the invention aims to provide a borate sodium-ion battery cathode material with a chemical formula of CoNi2(BO3)2。
Further, it is an orthorhombic system and belongs to the Pnmn space group. The crystal structure is of the granular magnesium boron stone type.
The invention also aims to provide a preparation method of the borate sodium-ion battery cathode material, which comprises the steps of uniformly mixing a nickel source, a cobalt source and a boron source according to the molar ratio of 2:1: 2-3, sintering and preserving heat in an oxidizing atmosphere, and cooling to obtain a target product pure-phase CoNi2(BO3)2。
Furthermore, the molar ratio of the nickel source to the cobalt source to the boron source is 2:1: 2-2.5. Dry grinding or wet grinding and mixing for 2-4 h; and then sintering in air. If the nickel source and the cobalt source are not in the limited range of the invention, pure phase target products cannot be formed; if the content of the boron source is too low, a pure-phase target product cannot be formed; if the content of the boron source is too high, waste of raw materials and difficulty in removing excess boron are caused.
Further, the oxidizing atmosphere is under an air or oxygen atmosphere. Preferably under an air atmosphere.
Furthermore, the sintering temperature is 800-. Furthermore, the sintering temperature is 800-. The sintering temperature is moderate, and if the temperature is too low, pure-phase Co cannot be prepared2Ni(BO3)2Materials, Co possibly produced if the temperature is too high2Ni(BO3)2The material particles are enlarged, which is not beneficial to ion transmission and electrolyte infiltration, and reduces the electrochemical performance of the material.
Furthermore, the heating rate is controlled to be 1-20 ℃/min during the sintering process.
Further, the nickel source is any one or combination of nickel oxide, nickel oxalate, nickel nitrate, nickel chloride or nickel sulfate;
the cobalt source is any one or combination of cobaltosic oxide, cobalt oxalate, cobalt nitrate, cobalt sulfate or cobalt oxide;
the boron source is selected from any one or combination of a plurality of boron trioxide, boric acid, boron nitride, ammonia borate or phenylboronic acid.
The invention also aims to provide application of the borate sodium-ion battery negative electrode material in a sodium-ion battery, wherein the sodium-ion battery consists of a working electrode, a counter electrode, electrolyte and a diaphragm, and the working electrode material is CoNi2(BO3)2。
Compared with the prior art, the CoNi of the invention2(BO3)2The material has the characteristics of simple preparation process flow, low requirement on the performance of equipment, high product purity and the like. Produced CoNi2(BO3)2The material has high specific capacity and rate capability, and is a sodium ion battery cathode material with application potential.
Drawings
FIG. 1 shows CoNi prepared in example 1 and comparative example 12(BO3)2An XRD pattern of the material;
FIG. 2 shows CoNi prepared in example 12(BO3)2Charge-discharge curves for the material at times 1, 2 and 3;
FIG. 3 shows CoNi prepared in example 12(BO3)2Cycling performance plots of the materials at a current density of 200 mA/g.
FIG. 4 shows CoNi prepared in example 12(BO3)2And (3) a rate performance graph of the material under different electric current densities.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
CoNi synthesized by the method of the invention2(BO3)2Negative electrode material, conductive carbon black and binderUniformly mixing carboxymethyl cellulose (CMC) according to a mass ratio of 80:10:10, coating the mixture on a copper foil, drying, punching into a negative plate, and drying at 80 ℃ for 24 hours.
Taking metallic sodium as a counter negative electrode; dissolving in a solvent with the mass ratio of 1mol/L as 1:1 of NaClO in a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC)4Salt solution is used as electrolyte; and assembling the button cell in an argon glove box.
The electrochemical performance test is carried out by adopting a Wuhan blue electricity CT2001A type battery tester, and the charging and discharging voltage range is 0.01V-3.0V (vs. Na)+Na). The test temperature was 25 ℃.
Both nickel nitrate and cobalt nitrate in the following examples are hexahydrate salts.
Example 1
Uniformly mixing about 3g of nickel nitrate, about 1.5g of cobalt nitrate and about 0.7g of boric acid by grinding, heating to 900 ℃ at the speed of 5 ℃/min in a tube furnace under the air atmosphere condition, keeping the temperature for 48 hours, and naturally cooling to room temperature to obtain a product CoNi2(BO3)2A material.
Comparative example 1
Uniformly mixing about 3g of nickel nitrate, about 1.5g of cobalt nitrate and about 0.7g of boric acid by grinding, heating to 750 ℃ at the speed of 5 ℃/min in a tube furnace under the air atmosphere condition, keeping the temperature for 48 hours, and naturally cooling to room temperature to obtain a product CoNi2(BO3)2A material.
From the XRD pattern (FIG. 1), CoNi prepared in example 1 was observed2(BO3)2Materials, and CoNi reported in the literature2(BO3)2The structures of the two phases are identical, and the components of the prepared material are pure-phase CoNi2(BO3)2. The product obtained by calcination at 750 ℃ in comparative example 1 had Co3BO5When the impurities are not in the experimental temperature range, pure-phase CoNi cannot be synthesized2(BO3)2. FIG. 2 shows CoNi2(BO3)2The 1 st, 2 nd and 3 rd charge-discharge curves of the material are shown in the figure, and the charge-discharge voltage range of 0.01-3.0V is in the first charge-discharge voltage rangeIn the discharging process, an obvious discharging platform is formed, and the same platform does not appear in the second discharging process, which shows that the material has structural change in the first charging and discharging process, and in the subsequent charging and discharging process, the charging and discharging curves are basically overlapped, which shows that the subsequent circulating structure is kept stable, and the good circulating life is favorably kept. FIG. 3 shows CoNi2(BO3)2The cycle performance diagram of the material under the charge-discharge current density of 200mA/g is shown in the figure, the 2 nd discharge capacity is 461.3mA/g, and CoNi is obtained after 30 cycles2(BO3)2The capacity of (2) was maintained at 368.2 mA/g. FIG. 4 is a graph showing the rate capability of the material, and it can be seen that the capacities of the cobalt-nickel protoborate negative electrodes were 459.1mAh/g, 321.7mAh/g, 271.5mAh/g, and 222.5mAh/g, respectively, when the discharge current densities were 200mA/g, 500mA/g, 1000mA/g, and 2000 mA/g. The material is used for the sodium ion battery and has excellent rate performance.
Example 2
Uniformly mixing about 5.8g of nickel nitrate, about 2.9g of cobalt nitrate and about 1.24g of boric acid by grinding, heating to 1000 ℃ at the speed of 1 ℃/min in a tube furnace under the air atmosphere condition, keeping the temperature for 55 hours, and naturally cooling to room temperature to obtain a pure-phase impurity-free product CoNi2(BO3)2A material.
Example 3
Uniformly mixing about 6g of nickel nitrate, about 3g of cobalt nitrate and about 1.4g of boric acid by grinding, heating to 900 ℃ at the speed of 3 ℃/min in a tube furnace under the condition of oxygen atmosphere, keeping the temperature for 48 hours, and naturally cooling to room temperature to obtain a pure-phase impurity-free product CoNi2(BO3)2A material.
Example 4
Uniformly mixing about 3g of nickel nitrate, about 1.5g of cobalt nitrate and about 0.7g of boric acid by grinding, heating to 1100 ℃ at the speed of 3 ℃/min in a tube furnace under the air atmosphere condition, keeping the temperature for 48 hours, and naturally cooling to room temperature to obtain a pure-phase impurity-free product CoNi2(BO3)2A material.
Example 5
About 3g of nitric acidUniformly mixing nickel, about 1.5g of cobalt nitrate and about 0.7g of boric acid by grinding, heating to 1200 ℃ at the speed of 5 ℃/min in a tube furnace under the air atmosphere condition, keeping the temperature for 55 hours, and naturally cooling to room temperature to obtain a pure-phase impurity-free product CoNi2(BO3)2A material.
Example 6
Uniformly mixing about 5.8g of nickel nitrate, about 2.9g of cobalt nitrate and about 1.24g of boric acid by grinding, heating to 1200 ℃ at the speed of 3 ℃/min in a tube furnace under the air atmosphere condition, keeping the temperature for 48 hours, and naturally cooling to room temperature to obtain a pure-phase impurity-free product CoNi2(BO3)2A material.
Example 7
Taking nickel oxide, cobaltosic oxide and boron trioxide, ensuring the molar ratio of nickel to cobalt to boron to be 2:1:2, grinding and mixing uniformly, heating to 950 ℃ at the speed of 1 min/DEG C in a tubular furnace in the air atmosphere, preserving heat for 60h, and naturally cooling to obtain a pure-phase impurity-free product CoNi2(BO3)2A material.
Example 8
Taking nickel oxalate, cobalt oxalate and boron nitride, ensuring that the molar ratio of nickel to cobalt to boron is 2:1:3, grinding and mixing uniformly, heating to 1200 ℃ at the speed of 20 min/DEG C in a tubular furnace under the air atmosphere, preserving heat for 1h, and naturally cooling to obtain a pure-phase impurity-free product CoNi2(BO3)2A material.
Example 9
Taking nickel chloride, cobalt sulfate and ammonia borate, ensuring that the molar ratio of nickel to cobalt to boron is 2:1:2.5, grinding and mixing uniformly, heating to 1100 ℃ at the speed of 10 min/DEG C in a tubular furnace under the air atmosphere, preserving heat for 20h, and naturally cooling to obtain a pure-phase impurity-free product CoNi2(BO3)2A material.
Example 10
Taking nickel sulfate, cobalt oxide and phenylboronic acid, ensuring that the molar ratio of nickel to cobalt to boron is 2:1:2.8, grinding and mixing uniformly, heating to 800 ℃ at the speed of 10 min/DEG C in a tubular furnace in the air atmosphere, preserving heat for 48h, naturally cooling, and then obtaining the productObtaining pure-phase product CoNi without impurities2(BO3)2A material.
Example 11
Taking a mixture of nickel sulfate and nickel nitrate (the mass ratio of the nickel sulfate to the nickel nitrate is 1:1), a mixture of cobalt nitrate and cobalt sulfate (the mass ratio of the cobalt nitrate to the cobalt sulfate is 1:1), and a mixture of boron trioxide and boron nitride (the mass ratio of the boron trioxide to the boron nitride is 1:1), ensuring that the molar ratio of nickel to cobalt to boron is 2:1:2.8, grinding and uniformly mixing, heating to 900 ℃ at the speed of 10 min/DEG C in a tubular furnace in the air atmosphere, preserving heat for 40h, and naturally cooling to obtain a pure-phase impurity-free product CoNi2(BO3)2A material.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (6)

1.一种硼酸盐类钠离子电池负极材料在钠离子电池中的应用，其特征在于，钠离子电池由工作电极、对电极、电解液及隔膜组成，工作电极材料为电池负极材料CoNi2(BO3)2；1. the application of a borate type sodium ion battery negative material in sodium ion battery, it is characterized in that, sodium ion battery is made up of working electrode, counter electrode, electrolyte and separator, and working electrode material is battery negative material CoNi 2 ( BO 3 ) 2 ; 该电池负极材料的制备方法具体为：The preparation method of the negative electrode material of the battery is as follows: 将镍源、钴源和硼源以摩尔比2:1:2～3混合均匀，于氧化性气氛下烧结保温，冷却后即得到目的产物；The nickel source, the cobalt source and the boron source are uniformly mixed in a molar ratio of 2:1:2-3, sintered and kept in an oxidizing atmosphere, and the target product is obtained after cooling; 烧结温度为800-1200℃，时间为1-60h。The sintering temperature is 800-1200℃, and the time is 1-60h. 2.根据权利要求1所述的一种硼酸盐类钠离子电池负极材料的应用，其特征在于，其为正交晶系，属于Pnmn空间群。2 . The application of a borate-based sodium-ion battery negative electrode material according to claim 1 , wherein it is an orthorhombic system and belongs to the Pnmn space group. 3 . 3.根据权利要求1所述的一种硼酸盐类钠离子电池负极材料的应用，其特征在于，氧化性气氛为在空气或氧气气氛下。3. the application of a kind of borate sodium ion battery negative electrode material according to claim 1, is characterized in that, oxidizing atmosphere is under air or oxygen atmosphere. 4.根据权利要求1所述的一种硼酸盐类钠离子电池负极材料的应用，其特征在于，烧结温度为800-1100℃，时间为20-60h。4 . The application of a borate-based sodium-ion battery negative electrode material according to claim 1 , wherein the sintering temperature is 800-1100° C. and the time is 20-60 h. 5 . 5.根据权利要求1所述的一种硼酸盐类钠离子电池负极材料的应用，其特征在于，烧结过程中，升温速率控制为1-20℃/min。5 . The application of a borate-based sodium-ion battery negative electrode material according to claim 1 , wherein, in the sintering process, the temperature increase rate is controlled to be 1-20° C./min. 6 . 6.根据权利要求1所述的一种硼酸盐类钠离子电池负极材料的应用，其特征在于，所述的镍源为氧化镍、草酸镍、硝酸镍、氯化镍或者硫酸镍中的任意一种或者几种的组合；6. the application of a kind of borate sodium ion battery negative electrode material according to claim 1, is characterized in that, described nickel source is any in nickel oxide, nickel oxalate, nickel nitrate, nickel chloride or nickel sulfate one or a combination of several; 所述的钴源为四氧化三钴、草酸钴、硝酸钴、硫酸钴或者氧化钴中的任意一种或者几种的组合；The cobalt source is any one or a combination of cobalt tetroxide, cobalt oxalate, cobalt nitrate, cobalt sulfate or cobalt oxide; 所述的硼源选自三氧化二硼、硼酸、氮化硼、硼酸氨或苯硼酸中的任意一种或者几种的组合。The boron source is selected from any one or a combination of boron trioxide, boric acid, boron nitride, ammonium borate or phenylboronic acid.
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"Synthesis and Crystal Structure CoNi2(BO3)2";H. Güler et al.;《Inorganic Materials》;20090510;第45卷(第5期);第538页左栏第1段至第第540页右栏第1段 *

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