CN112408328A - A new type of lithium-ion battery ZrMn-based hydride composite negative electrode material and preparation method - Google Patents
A new type of lithium-ion battery ZrMn-based hydride composite negative electrode material and preparation method Download PDFInfo
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- 150000004678 hydrides Chemical class 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 23
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 23
- 238000003723 Smelting Methods 0.000 claims abstract description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 15
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000010405 anode material Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000011049 filling Methods 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 230000006698 induction Effects 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 12
- 239000011572 manganese Substances 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000011149 active material Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 6
- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012982 microporous membrane Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 239000008358 core component Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- CVMIVKAWUQZOBP-UHFFFAOYSA-L manganic acid Chemical compound O[Mn](O)(=O)=O CVMIVKAWUQZOBP-UHFFFAOYSA-L 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
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Abstract
本发明公开一种新型锂离子电池ZrMn基氢化物复合负极材料及制备方法，其具体特征在于：将纯金属锆和纯金属锰酸洗、除杂、烘干后进行熔炼获得ZrMn合金；将ZrMn合金粉碎后放入充氢罐中，充氢球磨处理可得到ZrMn氢化物；再将ZrMn氢化物和碳材料在玛瑙中研磨混合后放入充氢罐中充氢球磨二次处理，得到碳包覆ZrMn氢化物复合材料；本发明所制得的ZrMn基氢化物复合负极材料具有较高的放电比容量以及优异的倍率性能和循环稳定性，在500mA/g的电流密度下，经500次循环，放电比容量依然保持在500mAh/g，库伦效率高达99％；该制备工艺简单、易操作，可适用于工业规模化生产应用。所获得新型锂离子电池负极材料具有较高的容量和循环稳定性，具有较好的应用前景。
The invention discloses a novel ZrMn-based hydride composite negative electrode material for lithium ion batteries and a preparation method, which are specifically characterized in that: pure metal zirconium and pure metal manganese are pickled, impurity-removed, and dried to obtain ZrMn alloy; ZrMn alloy is obtained by smelting; After the alloy is pulverized, put it into a hydrogen-filled tank, and the ZrMn hydride can be obtained by ball-milling with hydrogen; then the ZrMn hydride and carbon material are ground and mixed in agate and put into a hydrogen-filled tank for secondary treatment with hydrogen-charged ball milling to obtain a carbon package. ZrMn hydride-coated composite material; the ZrMn-based hydride composite negative electrode material prepared by the invention has high discharge specific capacity, excellent rate performance and cycle stability, and can be cycled for 500 times at a current density of 500mA/g , the discharge specific capacity is still maintained at 500mAh/g, and the coulombic efficiency is as high as 99%; the preparation process is simple and easy to operate, and can be applied to industrial-scale production applications. The obtained new anode material for lithium ion battery has high capacity and cycle stability, and has good application prospect.
Description
Technical Field
The invention relates to the field of lithium ion battery electrode materials, in particular to a novel ZrMn based hydride composite anode material of a lithium ion battery and a preparation method thereof.
Background
With the vigorous development of new energy automobiles in China, the research on developing high-capacity lithium ion batteries to meet the requirements of power systems of electric automobiles is urgent. As a core component of the lithium ion battery, the performance of the electrode material has a great influence on the energy and power density of the lithium ion battery. Improving the electrochemical performance of electrode materials and developing new electrode materials are important ways to improve the performance of lithium ion batteries. The current commercial graphite cathode is difficult to meet the requirements of people due to the limit of the capacity of the graphite cathode. Therefore, the development of a novel negative electrode material with high energy density to replace a graphite negative electrode has important significance in promoting the development of lithium ion batteries.
Metal hydrides are one of the most promising negative electrode materials for lithium ion batteries because of their high theoretical specific capacity, lower operating voltage, environmental friendliness, and low cost. Despite these advantages, this material has problems of large volume expansion and poor conductivity during charge and discharge.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
In order to solve the technical defects, the invention adopts the technical scheme that the preparation method of the novel ZrMn based hydride composite anode material of the lithium ion battery comprises the following steps:
s1, smelting: at room temperature, carrying out acid cleaning, impurity removal and drying on pure zirconium and pure manganese, and then smelting to obtain the ZrMn alloy;
s2, hydrogenation ball milling: the ZrMn alloy is crushed and then placed into a hydrogen filling tank, and hydrogen filling and ball milling are carried out for hydrogenation treatment to obtain ZrMn hydride;
s3, mechanical mixing: and grinding and mixing the ZrMn hydride and the carbon material in agate, and putting the mixture into a hydrogen charging tank for hydrogen charging and ball milling to obtain the carbon-coated ZrMn hydride composite material, wherein the carbon-coated ZrMn hydride composite material is the novel ZrMn-based hydride composite negative electrode material of the lithium ion battery.
Preferably, in step S1, the molar percentage of the pure zirconium metal and the pure manganese metal is 1: 1.5-2.1.
Preferably, in step S1, the melting of the ZrMn alloy is performed by high-frequency induction melting under the protection of argon, the power of the high-frequency induction melting is 15KW to 18KW, and the melting time is 80S to 100S.
Preferably, the hydrogen pressure of the hydrogenation treatment in the step S2 is 3MPa to 5MPa, and the hydrogen pressure of the hydrogenation treatment in the step S3 is 1MPa to 2 MPa.
Preferably, the carbon material is one of graphite, carbon nanotube and graphene.
Preferably, in the step S3, the mass percentage of the ZrMn hydride to the carbon material is 70% to 80% to 20% to 30%.
Preferably, in step S2, the mechanical ball milling process parameters are set as follows: the ball-material ratio is 60: 1, the ball milling rotation speed is 400rpm, and the ball milling time is 2 h-5 h.
Preferably, in step S3, the mechanical ball milling process parameters are set as follows: the ball-material ratio is 40: 1, the ball milling rotating speed is 300 rpm-400 rpm, and the ball milling time is 2 hours.
Preferably, the carbon-coated ZrMn hydride composite negative electrode material is prepared by the preparation method of the novel ZrMn hydride composite negative electrode material for the lithium ion battery, and the carbon-coated ZrMn hydride composite negative electrode material is the novel ZrMn hydride composite negative electrode material for the lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that: the ZrMn based hydride composite material prepared by the invention can be used as a negative active material of a lithium ion battery. The material has excellent cycle performance and specific capacity, and has simple preparation process, low equipment requirement and short production period; the ZrMn-based hydride composite active material can be simply and feasibly prepared by the method, and has the advantages that the composite material realizes the strong coupling effect between the ZrMn-based hydride and the carbon material, the ZrMn-based hydride has higher specific discharge capacity, the carbon material improves the conductivity of the ZrMn-based hydride, and the ZrMn-based hydride composite active material has excellent electrochemical performance when being used as an electrode material of a lithium ion battery, so that the ZrMn-based hydride composite active material has wide application prospect in the fields of various new energy sources and new materials such as energy storage materials, advanced functional material preparation and the like.
Drawings
FIG. 1 is an XRD spectrum of the product of each step in example one of the present invention;
FIG. 2 is an SEM spectrum of a ZrMn based hydride composite material in the first embodiment of the present invention;
FIG. 3 is a CV diagram of a ZrMn based hydride composite material in a first embodiment of the present invention;
FIG. 4 is a graph showing the charging and discharging curves of the ZrMn based hydride composite material at a current density of 100mA/g in the first embodiment of the present invention;
FIG. 5 is a graph showing the rate capability of a ZrMn based hydride composite material in the first embodiment of the present invention;
FIG. 6 is a graph showing the cycle performance of a ZrMn based hydride composite at a current density of 500mA/g in one embodiment of the present invention;
FIG. 7 is a resistance diagram of a ZrMn based hydride composite material in an embodiment of the present invention.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
The invention relates to a preparation method of a novel ZrMn-based hydride composite anode material of a lithium ion battery, which comprises the following steps:
s1, preparation of ZrMn alloy: washing pure zirconium and manganic acid at room temperature to remove impurities and drying, weighing the pure zirconium and manganese after acid washing according to a certain mole percentage, and smelting;
s2, preparation of ZrMn hydride: and (4) crushing the ZrMn alloy obtained in the step (S1), putting the crushed ZrMn alloy into a hydrogen filling tank, performing hydrogen filling ball milling, and performing hydrogenation treatment to obtain ZrMn hydride, wherein the mechanical ball milling process parameters are as follows: the ball-material ratio is 60: 1, the ball milling rotation speed is 400rpm, and the ball milling time is 2 h-5 h.
S3, preparation of ZrMn hydride composite material: weighing ZrMn hydride and carbon materials prepared in the step S2 according to a certain mass percentage, grinding and uniformly mixing the ZrMn hydride and the carbon materials in agate, then putting the uniformly mixed product into a hydrogen filling tank for hydrogen filling and ball milling treatment to obtain the carbon-coated ZrMn hydride composite material, wherein the mechanical ball milling process parameters are as follows: the ball-material ratio is 40: 1, the ball milling rotating speed is 300 rpm-400 rpm, and the ball milling time is 2 hours.
In step S1, the mol percent of Zr and Mn is 1: 1.5-2.1.
The smelting of the ZrMn alloy is high-frequency induction smelting under the protection of argon, wherein the power is controlled to be 15 KW-18 KW, and the smelting time is 80 s-100 s.
The hydrogen pressures in the hydrogenation treatment in step S2 and step S3 are 3MPa to 5MPa and 1MPa to 2MPa, respectively.
The carbon material is one of graphite, carbon nano tube and graphene.
The mass percentage of ZrMn hydride to carbon material is 70% -80% to 20% -30%.
The carbon-coated ZrMn-based hydride composite negative electrode material is prepared by the preparation method of the novel ZrMn-based hydride composite negative electrode material of the lithium ion battery.
After 500 cycles of charge and discharge under the current density of 500mA/g, the ZrMn-based hydride composite negative electrode material still keeps the specific discharge capacity at 450mAh/g, and the coulombic efficiency is up to 99%.
The ZrMn based hydride composite material prepared by the invention can be used as a negative active material of a lithium ion battery. The material has excellent cycle performance and specific capacity, simple preparation process, low equipment requirement and short production period. The test was carried out with a lithium metal sheet as the negative electrode, a polypropylene microporous membrane Celgard2400 as the separator, and a commercial electrolyte (LiPF)6As electrolyte, EC and DMC were solvents and volume ratio was 1: 1), assembled into CR2032 type button cell in a glove box.
The method can be used for simply and feasibly preparing the ZrMn-based hydride composite active material, and has the advantages that the composite material realizes the strong coupling effect between the ZrMn-based hydride and the carbon material, the ZrMn-based hydride has higher specific discharge capacity, the carbon material improves the conductivity of the ZrMn-based hydride, and the ZrMn-based hydride composite active material has excellent electrochemical performance when being used as an electrode material of a lithium ion battery, so that the ZrMn-based hydride composite active material has wide application prospect in the fields of various new energy sources and new materials such as energy storage materials, advanced functional material preparation and the like.
The following is illustrated by specific examples:
example one
The preparation method of the ZrMn-based hydride active material comprises the following steps:
s1, preparation of ZrMn alloy:
at room temperature, metal zirconium blocks and manganese sheets with the purity of 99% are washed for 3 minutes by 10% diluted hydrochloric acid, then washed and dried by deionized water, 20g of zirconium and manganese are respectively weighed according to the mol percentage of 1: 2, the zirconium and manganese are put into a high-frequency induction smelting furnace, argon is introduced for protection to carry out smelting, the power of the smelting furnace is regulated and controlled at 16KW, and the time is 80 s.
S2, preparation of ZrMn hydride:
the ZrMn alloy is crushed, 2g of ZrMn alloy powder is weighed and placed in a hydrogen filling tank, 3Mpa hydrogen is filled in the hydrogen filling tank for ball milling treatment, and ZrMn hydride is obtained, wherein the mechanical ball milling technological parameters are as follows: the ball-material ratio is 60: 1, the ball milling rotation speed is 400rpm, and the ball milling time is 2 h.
S3, preparation of ZrMn hydride composite material:
weighing 200mg of ZrMn hydride prepared in S2 and graphene according to the mass percent of 75: 25, grinding and uniformly mixing in agate, then putting the uniformly mixed product into a hydrogen charging tank, charging 2Mpa of hydrogen, and carrying out ball milling treatment to obtain the graphene-coated ZrMn hydride composite material, wherein the mechanical ball milling technological parameters are as follows: the ball-material ratio is 40: 1, the ball milling rotation speed is 400rpm, and the ball milling time is 2 h. An SEM image of the graphene-coated ZrMn hydride composite material is shown in fig. 2.
Phase XRD patterns of the ZrMn alloy, the ZrMn hydride and the ZrMn hydride composite material are shown in figure 1, and the product does not generate phase change and impurity substances. Wherein, the SEM image of the ZrMn hydride composite material is shown in fig. 2, and the ZrMn hydride is coated by graphene.
The graphene-coated ZrMn hydride composite material is used as an active electrode of a lithium ion battery, a metal lithium sheet is used as a negative electrode, a polypropylene microporous membrane Celgard2400 is used as a diaphragm, and a commercial electrolyte (LiPF)6As electrolyte, EC and DMC were solvents and volume ratio was 1: 1), assembled into CR2032 type button cell in a glove box.
As shown in FIG. 3, the cyclic voltammogram has a lower first-turn reduction peak, a weaker redox peak, good coincidence of the second and third curves, and less irreversible lithium ion loss at a sweep rate of 0.1 mV/s.
FIG. 4 is a charging and discharging curve diagram under the current density of 100mA/g and in the range of 0.01V to 3V, the first discharging specific capacity is up to 890mAh/g, the charging specific capacity is 620mAh/g, the first-turn coulombic efficiency is 70%, and the high discharging specific capacity is shown.
FIG. 5 shows the rate capability of ZrMn hydride composites at different current densities, with specific discharge capacities changing from 634.6mAh/g, 490mAh/g, 390.2mAh/g, 310.6mAh/g to 240.8mAh/g at current densities of 100mAh/g, 200mAh/g, 500mAh/g, 1000mAh/g to 2000 mAh/g. When the current density is recovered to 100mAh/g, the specific discharge capacity can be recovered to 606.2mAh/g, which indicates that the ZrMn hydride composite material has better reversibility.
Example two
The preparation method of the ZrMn based hydride composite active material comprises the following steps:
s1, preparation of ZrMn alloy:
at room temperature, metal zirconium blocks and manganese sheets with the purity of 99% are washed for 3 minutes by 10% diluted hydrochloric acid, then washed and dried by deionized water, 20g of zirconium and manganese are respectively weighed according to the mol percentage of 1: 1.5, the zirconium and manganese are put into a high-frequency induction smelting furnace, argon is introduced for protection to carry out smelting, the power of the smelting furnace is controlled at 18KW, and the time is 90 s.
S2, preparation of ZrMn hydride:
the ZrMn alloy is crushed, 2g ZrMn alloy powder is weighed and placed in a hydrogen filling tank, 4Mpa hydrogen is filled in the hydrogen filling tank for ball milling treatment to obtain ZrMn hydride, and the mechanical ball milling technological parameters are as follows: the ball-material ratio is 60: 1, the ball milling rotation speed is 400rpm, and the ball milling time is 2 h.
S3, preparation of ZrMn hydride composite material:
weighing 200mg of ZrMn hydride prepared in the step (2) and graphene according to the mass percentage of 80: 20, grinding and uniformly mixing in agate, then putting the uniformly mixed product into a hydrogen tank filled with 1Mpa, and performing hydrogen charging and ball milling treatment to obtain the graphene coated ZrMn hydride composite material, wherein the mechanical ball milling technological parameters are as follows: the ball-material ratio is 40: 1, the ball milling rotation speed is 400rpm, and the ball milling time is 2 h.
The graphene-coated ZrMn hydride composite material is used as an active electrode of a lithium ion battery, a metal lithium sheet is used as a negative electrode, a polypropylene microporous membrane Celgard2400 is used as a diaphragm, and a commercial electrolyte (LiPF)6As electrolyte, EC and DMC were solvents and volume ratio was 1: 1), assembled into CR2032 type button cell in a glove box.
Comparative example 1
S1, preparation of ZrMn alloy:
at room temperature, metal zirconium blocks and manganese sheets with the purity of 99% are washed for 3 minutes by 10% diluted hydrochloric acid, then washed and dried by deionized water, 20g of zirconium and manganese are respectively weighed according to the mol percentage of 1: 2, the zirconium and manganese are put into a high-frequency induction smelting furnace, argon is introduced for protection to carry out smelting, the power of the smelting furnace is regulated and controlled at 16KW, and the time is 80 s.
S2, preparation of ZrMn hydride:
the ZrMn alloy is crushed, 2g ZrMn alloy powder is weighed and placed in a hydrogen filling tank, 4Mpa hydrogen is filled in the hydrogen filling tank for ball milling treatment to obtain ZrMn hydride, and the mechanical ball milling technological parameters are as follows: the ball-material ratio is 60: 1, the ball milling rotation speed is 400rpm, and the ball milling time is 2 h.
ZrMn hydride material is used as lithium ion batteryA lithium metal sheet as a negative electrode, a U.S. Cellgard series separator, and a commercial electrolyte (LiPF)6As electrolyte, EC and DMC were solvents and volume ratio was 1: 1), assembled into CR2032 type button cell in a glove box.
By comparison between examples and comparative examples:
after 500 cycles of charge and discharge, the coulombic efficiency with the specific discharge capacity of 450mAh/g can reach 99%, the capacity decay is slow, the corresponding electrochemical stability is good (figure 6, the current density is 500mA/g), and compared with a ZrMn hydride active material, the capacity is improved by about 8 times.
The electrochemical impedance spectrum is shown in fig. 7, after the graphene is introduced, the impedance of the ZrMn hydride composite material is reduced, the conductivity is greatly improved, and the dynamic performance is improved.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a novel ZrMn based hydride composite anode material of a lithium ion battery is characterized by comprising the following steps:
s1, smelting: at room temperature, carrying out acid cleaning, impurity removal and drying on pure zirconium and pure manganese, and then smelting to obtain a ZrMn alloy;
s2, hydrogenation ball milling: the ZrMn alloy is crushed and then placed into a hydrogen filling tank, and hydrogen filling and ball milling are carried out for hydrogenation treatment to obtain ZrMn hydride;
s3, mechanical mixing: and grinding and mixing the ZrMn hydride and the carbon material in agate, and then putting the mixture into a hydrogen charging tank for hydrogen charging and ball milling treatment to obtain the carbon-coated ZrMn hydride composite material, wherein the carbon-coated ZrMn hydride composite material is the novel ZrMn-based hydride composite negative electrode material of the lithium ion battery.
2. The method for preparing the ZrMn based hydride composite anode material of the lithium ion battery as claimed in claim 1, wherein in step S1, the molar percentage of the pure zirconium metal and the pure manganese metal is 1: 1.5-2.1.
3. The method for preparing a ZrMn-based hydride composite negative electrode material of a lithium ion battery as claimed in claim 2, wherein in step S1, the ZrMn alloy is melted by high-frequency induction melting under the protection of argon, the power of the high-frequency induction melting is 15KW to 18KW, and the melting time is 80S to 100S.
4. The method for preparing a ZrMn-based hydride composite negative electrode material for a lithium ion battery as claimed in claim 1, wherein the hydrogen pressures for the hydrotreatment in the step S2 are respectively 3MPa to 5 MPa.
5. The method for preparing a ZrMn-based hydride composite negative electrode material for a lithium ion battery as claimed in claim 1, wherein the hydrogen pressure of the hydrogenation treatment in the step S3 is 1MPa to 2 MPa.
6. The method for preparing the ZrMn based hydride composite anode material of the lithium ion battery as claimed in claim 1, wherein the carbon material is one of graphite, carbon nanotube and graphene.
7. The method for preparing a ZrMn-based hydride composite anode material for a lithium ion battery as claimed in claim 1, wherein in the step S3, the mass percentage of the ZrMn hydride to the carbon material is 70% to 80%: 20 to 30 percent.
8. The method for preparing a ZrMn-based hydride composite negative electrode material of a lithium ion battery as claimed in claim 1, wherein in step S2, the mechanical ball milling process parameters are set as follows: the ball-material ratio is 60: 1, the ball milling rotation speed is 400rpm, and the ball milling time is 2 h-5 h.
9. The method for preparing a ZrMn-based hydride composite negative electrode material of a lithium ion battery as claimed in claim 1, wherein in step S3, the mechanical ball milling process parameters are set as follows: the ball-material ratio is 40: 1, the ball milling rotating speed is 300 rpm-400 rpm, and the ball milling time is 2 hours.
10. A novel ZrMn-based hydride composite negative electrode material for a lithium ion battery, characterized in that the carbon-coated ZrMn hydride composite negative electrode material prepared by the method for preparing a novel ZrMn-based hydride composite negative electrode material for a lithium ion battery according to any one of claims 1 to 8 is the novel ZrMn-based hydride composite negative electrode material for a lithium ion battery.
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