CN109850955B - Negative electrode material ZnCo of lithium ion battery2O4Method for preparing nano-rod - Google Patents
Negative electrode material ZnCo of lithium ion battery2O4Method for preparing nano-rod Download PDFInfo
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- 239000002073 nanorod Substances 0.000 title claims abstract description 42
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 229910003119 ZnCo2O4 Inorganic materials 0.000 claims abstract description 61
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 5
- 150000003751 zinc Chemical class 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- YZYASTRURKBPPS-UHFFFAOYSA-N C(CCC(=O)OCCCCCC(C)C)(=O)OCCCCCC(C)C.[Na] Chemical compound C(CCC(=O)OCCCCCC(C)C)(=O)OCCCCCC(C)C.[Na] YZYASTRURKBPPS-UHFFFAOYSA-N 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 238000001953 recrystallisation Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 23
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MQKXWEJVDDRQKK-UHFFFAOYSA-N bis(6-methylheptyl) butanedioate Chemical compound CC(C)CCCCCOC(=O)CCC(=O)OCCCCCC(C)C MQKXWEJVDDRQKK-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- HWQXBVHZYDELQG-UHFFFAOYSA-L disodium 2,2-bis(6-methylheptyl)-3-sulfobutanedioate Chemical compound C(CCCCC(C)C)C(C(C(=O)[O-])S(=O)(=O)O)(C(=O)[O-])CCCCCC(C)C.[Na+].[Na+] HWQXBVHZYDELQG-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- -1 octyl phenyl Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a negative electrode material ZnCo of a lithium ion battery2O4Firstly, dissolving zinc salt and cobalt salt in an organic solvent according to a molar ratio of 1:2, and dissolving a surfactant in the organic solvent to obtain a colorless transparent solution; then placing the colorless transparent solution into a reaction container, carrying out reflux reaction for 3-10h under the condition of magnetic stirring at the temperature of 60-150 ℃ to obtain white precipitate, and cleaning the white precipitate to obtain ZnCo2O4Precursor, finally ZnCo2O4Calcining the precursor in air atmosphere to obtain ZnCo2O4And (4) nanorods. The invention prepares ZnCo with a one-dimensional porous structure by a reflux recrystallization method2O4The nano-rod has a one-dimensional structure which can shorten a lithium ion diffusion path, and a porous structure which can inhibit volume strain in the charge and discharge process so as to improve ZnCo2O4Electrochemical properties of the negative electrode material.
Description
Technical Field
The invention relates to the field of battery material preparation, in particular to a negative electrode material ZnCo of a lithium ion battery2O4A method for preparing nano-rods.
Background
With the wide application of lithium ion batteries in the field of power batteries, the requirements on the energy density of the lithium ion batteries are higher and higher. Therefore, electrode materials with high specific capacity, high rate capability and long cycle life have received much attention. The graphite cathode is used as the main material of the current lithium ion battery cathode material and has low theoretical capacity (374 mAh g)-1) And cannot meet the requirements of the current development. It is therefore necessary to find better alternative anode materials. Wherein, the binary transition gold with spinel structureThe interest of researchers has been raised by the generic oxide materials due to their higher theoretical capacity.
In the Co-based binary transition metal oxides, ZnCo2O4It is of great interest because of its lower cost, high thermal stability, lower toxicity and higher theoretical capacity. Zn during discharge2+The reduction to Zn and the resulting Zn can form a Li/Zn alloy with Li, which can provide additional discharge capacity during alloying. ZnCo2O4The electrode material also has many problems to be solved, such as low conductivity, large volume change during charge and discharge, and the like. The main method for solving the problems at present is to design structures, such as hollow spheres, core-shell structures, nanorods and the like, and provide more reactive sites by shortening ion diffusion paths and increasing the specific surface area of materials, so as to inhibit the volume strain of the materials.
Disclosure of Invention
The invention aims to solve the technical problem of providing a negative electrode material ZnCo of a lithium ion battery2O4Preparation method of nano rod, namely preparation of ZnCo with one-dimensional porous structure by reflux recrystallization2O4The nano-rod has a one-dimensional structure which can shorten a lithium ion diffusion path, and a porous structure which can inhibit volume strain in the charge and discharge process so as to improve ZnCo2O4Electrochemical properties of the negative electrode material.
The technical scheme of the invention is as follows:
negative electrode material ZnCo of lithium ion battery2O4The preparation method of the nano rod specifically comprises the following steps:
(1) dissolving zinc salt and cobalt salt in an organic solvent according to a molar ratio of 1:2, and then dissolving a surfactant in the organic solvent;
(2) putting the solution obtained in the step (1) into a reaction container, performing reflux reaction for 3-10h under the condition of magnetic stirring at the temperature of 60-150 ℃ to obtain white precipitate, and cleaning the white precipitate to obtain ZnCo2O4A precursor;
(3) ZnCo obtained in the step (2)2O4Calcining the precursor in air atmosphere to obtain ZnCo2O4The nano-rod, wherein the calcining temperature is 300-600 ℃, and the calcining time is 2-10 h.
The zinc salt in the step (1) is at least one of zinc acetate, zinc nitrate, zinc sulfate and zinc chloride.
The cobalt salt in the step (1) is at least one of cobalt acetate, cobalt nitrate, cobalt sulfate and cobalt chloride.
The organic solvent in the step (1) is at least one of ethanol, ethylene glycol, isooctane, n-hexane, xylene and n-pentanol.
The surfactant in the step (1) is at least one of polyvinyl pyrrolidone, cetyl trimethyl ammonium bromide, sodium diisooctyl sulfosuccinate, sodium dodecyl sulfate and octyl phenyl polyvinyl ether.
In the step (2), the white precipitate is alternately cleaned for multiple times by adopting ethanol and distilled water, and is dried after being cleaned to obtain ZnCo2O4And (3) precursor.
The invention has the advantages that:
(1) the method has the advantages of simple preparation process, relatively mild reaction conditions and easy operation.
(2) The invention adopts surfactant as the carrier for nanorod production and adopts a reflux recrystallization method to prepare ZnCo with a one-dimensional porous structure2O4The nano-rod has a one-dimensional structure which can shorten a lithium ion diffusion path, and a porous structure which can inhibit volume strain in the charge and discharge process so as to improve ZnCo2O4Electrochemical properties of the negative electrode material.
(3) The ZnCo2O4 nano-rod prepared by the invention has loose surface and larger specific surface of porous structure, can increase the contact area with electrolyte so as to provide more active sites and be beneficial to improving the electrochemical performance, and the first discharge specific capacity of the ZnCo2O4 nano-rod is as high as 1121.1 mAh/g.
Drawings
Fig. 1 is a FESEM photograph of ZnCo2O4 precursor prepared in example 1 of the present invention.
FIG. 2 is an XRD pattern of ZnCo2O4 nanorods prepared in example 1 of the present invention.
FIG. 3 is a FESEM image of ZnCo2O4 nanorods prepared in example 1 of the invention.
FIG. 4 is a diagram of the electrochemical properties of ZnCo2O4 nanorods prepared in example 1 of the present invention.
Fig. 5 is a FESEM image of ZnCo2O4 material prepared in example 2 of the invention.
FIG. 6 is a graph of the electrochemical performance of the ZnCo2O4 material prepared in example 2 of the invention.
Fig. 7 is a FESEM image of ZnCo2O4 material prepared in example 3 of the invention.
FIG. 8 is a graph of the electrochemical performance of the ZnCo2O4 material prepared in example 3 of the invention.
Fig. 9 is a FESEM image of ZnCo2O4 material prepared in comparative example 1.
Fig. 10 is a graph of the electrochemical performance of the ZnCo2O4 material prepared in comparative example 1.
Fig. 11 is a FESEM image of ZnCo2O4 material prepared in comparative example 2.
Fig. 12 is a graph of the electrochemical performance of the ZnCo2O4 material prepared in comparative example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Negative electrode material ZnCo of lithium ion battery2O4The preparation method of the nano rod specifically comprises the following steps:
(1) dissolving 1 mmol of zinc acetate and 2 mmol of cobalt acetate in ethanol, and then dissolving polyvinyl pyrrolidone (PVP) in the ethanol to obtain colorless transparent solution;
(2) placing the colorless transparent solution into a three-neck round-bottom flask, carrying out reflux reaction for 5 hours under the condition of magnetic stirring at the temperature of 90 ℃ to obtain white precipitate, washing the white precipitate with hot ethanol and water for a plurality of times, and drying to obtain ZnCo with a one-dimensional structure2O4A precursor;
(3) ZnCo to be obtained2O4Calcining the precursor in air atmosphere to obtain ZnCo2O4The nano-rods are prepared, wherein the calcining temperature is 300 ℃, and the calcining time is 10 h.
See FIG. 1, FESEM photograph of ZnCo2O4 precursor, ZnCo obtained in step (2)2O4The precursor is composed of nano rods with the length of 3-5 mu m and the diameter of 200-250 nm.
Referring to FIG. 2, the XRD pattern of the prepared ZnCo2O4 nanorod is not clear, and the obvious impurity peak is not seen from the XRD pattern, which indicates that the prepared ZnCo2O4 nanorod is2O4The nano-rod is high-purity ZnCo2O 4.
Referring to FIG. 3, the obtained ZnCo2O4 nanorod has a FESEM image, in which the ZnCo2O4 nanorod has a nanorod structure with a length of about 2-4 μm and a diameter of 150-200 nm, and the surface of the nanorod has a loose porous structure.
Referring to fig. 4, the electrochemical performance of the prepared ZnCo2O4 nanorod is shown, the first specific discharge capacity of the ZnCo2O4 nanorod negative electrode material at a current density of 0.1C (1C =1000 mAh/g) reaches 1121.2 mAh/g, and the specific discharge capacities at current densities of 0.1C, 0.2C, 0.5C, 1C and 2C are 823.5 mAh/g, 783.5 mAh/g, 745.2 mAh/g, 615.2 mAh/g and 508.6 mAh/g, respectively.
Example 2
Negative electrode material ZnCo of lithium ion battery2O4The preparation method of the nano rod specifically comprises the following steps:
(1) dissolving 2 mmol of zinc nitrate and 4 mmol of cobalt nitrate in ethanol, and then dissolving Cetyl Trimethyl Ammonium Bromide (CTAB) in the ethanol to obtain colorless transparent solution;
(2) placing the colorless transparent solution into a three-neck round-bottom flask, performing reflux reaction for 6h under the condition of magnetic stirring at the temperature of 80 ℃ to obtain white precipitate, and performing reflux reaction on the white precipitate by using hot ethanol and waterWashing for several times and drying to obtain ZnCo with one-dimensional structure2O4A precursor;
(3) ZnCo to be obtained2O4Calcining the precursor in air atmosphere to obtain ZnCo2O4The nano-rods are prepared, wherein the calcining temperature is 600 ℃, and the calcining time is 2 hours.
Referring to fig. 5, a FESEM image of the prepared ZnCo2O4 material shows that the morphology of ZnCo2O4 is nanorod.
Referring to fig. 6, an electrochemical performance diagram of the ZnCo2O4 material shows that the first specific discharge capacity of the ZnCo2O4 negative electrode material at a current density of 0.1C (1C =1000 mAh/g) is 1042.1 mAh/g. Specific discharge capacities at current densities of 0.1C, 0.2C, 0.5C, 1C and 2C were 741.6 mAh/g, 713.4 mAh/g, 605.4 mAh/g, 507.4 mAh/g and 440.3 mAh/g, respectively.
Example 3
Negative electrode material ZnCo of lithium ion battery2O4The preparation method of the nano rod specifically comprises the following steps:
(1) dissolving 5 mmol of zinc sulfate and 10 mmol of cobalt sulfate in ethanol, and then dissolving diisooctyl succinate sodium sulfonate (NaAOT) in isooctane to obtain colorless transparent solution;
(2) placing the colorless transparent solution into a three-neck round-bottom flask, carrying out reflux reaction for 3 hours under the condition of magnetic stirring at the temperature of 100 ℃ to obtain white precipitate, washing the white precipitate with hot ethanol and water for a plurality of times, and drying to obtain ZnCo with a one-dimensional structure2O4A precursor;
(3) ZnCo to be obtained2O4Calcining the precursor in air atmosphere to obtain ZnCo2O4The nano-rods are prepared, wherein the calcining temperature is 500 ℃, and the calcining time is 3 h.
Referring to fig. 7, the FESEM of the prepared ZnCo2O4 material shows that the morphology of ZnCo2O4 is nanorod.
Referring to fig. 8, an electrochemical performance diagram of the ZnCo2O4 material shows that the first specific discharge capacity of the ZnCo2O4 negative electrode material at a current density of 0.1C (1C =1000 mAh/g) is 1070.7 mAh/g. Specific discharge capacities at current densities of 0.1C, 0.2C, 0.5C, 1C and 2C were 801.5 mAh/g, 762.3 mAh/g, 717.4 mAh/g, 588.1 mAh/g and 468.7 mAh/g, respectively.
Comparative example 1
Negative electrode material ZnCo of lithium ion battery2O4The preparation method specifically comprises the following steps:
(1) dissolving 1 mmol of zinc acetate and 2 mmol of cobalt acetate in ethanol;
(2) putting the solution obtained in the step (1) into a three-mouth round-bottom flask, carrying out reflux reaction for 5 hours under the condition of magnetic stirring at 90 ℃ to obtain white precipitate, washing the obtained white precipitate with hot ethanol and water for several times, and drying to obtain ZnCo2O4A precursor;
(3) ZnCo2O4Calcining the precursor in air atmosphere at 300 ℃ for 10h to obtain ZnCo2O4A material.
Referring to fig. 9, a FESEM of the prepared ZnCo2O4 material shows that the morphology of ZnCo2O4 has rod-like and block-like compositions with different sizes, i.e., a ZnCo2O4 nanorod structure cannot be formed without adding a surfactant.
Referring to fig. 10, an electrochemical performance diagram of the ZnCo2O4 material shows that the first specific discharge capacity of the ZnCo2O4 negative electrode material at a current density of 0.1C (1C =1000 mAh/g) is 995.2 mAh/g. Specific discharge capacities at current densities of 0.1C, 0.2C, 0.5C, 1C and 2C were 654.3 mAh/g, 632.2 mAh/g, 518.3 mAh/g, 443.9 mAh/g and 389.4 mAh/g, respectively.
Comparative example 2
Negative electrode material ZnCo of lithium ion battery2O4The preparation method specifically comprises the following steps:
(1) dissolving 1 mmol of zinc acetate and 2 mmol of cobalt acetate in ethanol, and then dissolving polyvinyl pyrrolidone (PVP) in the ethanol to obtain colorless transparent solution;
s2, placing the colorless transparent solution into a three-neck round-bottom flask, magnetically stirring at 90 ℃ until the solvent is completely evaporated to obtain a white precipitate, and washing the obtained white precipitate with hot ethanol and waterObtaining ZnCo after several times of drying2O4A precursor;
s3, mixing ZnCo2O4Calcining the precursor in air atmosphere at 300 ℃ for 10h to obtain ZnCo2O4A material.
Referring to fig. 11, a FESEM image of ZnCo2O4, it can be seen that ZnCo2O4 is composed of some particles and has no rod-like morphology, which indicates that ZnCo2O4 nanorods cannot be formed without using a reflux reaction, i.e., without using a reflux recrystallization method.
Referring to fig. 12, an electrochemical performance diagram of the ZnCo2O4 material, a first specific discharge capacity of the ZnCo2O4 material at a current density of 0.1C (1C =1000 mAh/g) is 935.2 mAh/g, and specific discharge capacities at current densities of 0.1C, 0.2C, 0.5C, 1C and 2C are 632.4 mAh/g, 573.4 mAh/g, 461.2 mAh/g, 257.4 mAh/g and 211.7 mAh/g, respectively.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. Negative electrode material ZnCo of lithium ion battery2O4The preparation method of the nano-rod is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) dissolving zinc salt and cobalt salt in an organic solvent according to a molar ratio of 1:2, and then dissolving a surfactant in the organic solvent; the organic solvent is ethanol or isooctane, and the surfactant is polyvinyl pyrrolidone, cetyl trimethyl ammonium bromide or sodium diisooctyl succinate sulfonate;
(2) putting the solution obtained in the step (1) into a reaction container, performing reflux reaction for 3-10h under the condition of magnetic stirring at the temperature of 60-150 ℃ to obtain white precipitate, and cleaning the white precipitate to obtain ZnCo2O4A precursor;
(3) ZnCo obtained in the step (2)2O4Precursor bodyCalcining in air atmosphere to obtain ZnCo2O4The nano-rod, wherein the calcining temperature is 300-600 ℃, and the calcining time is 2-10 h.
2. The negative electrode material ZnCo of claim 1 for lithium ion battery2O4The preparation method of the nano-rod is characterized by comprising the following steps: the zinc salt in the step (1) is at least one of zinc acetate, zinc nitrate, zinc sulfate and zinc chloride.
3. The negative electrode material ZnCo of claim 1 for lithium ion battery2O4The preparation method of the nano-rod is characterized by comprising the following steps: the cobalt salt in the step (1) is at least one of cobalt acetate, cobalt nitrate, cobalt sulfate and cobalt chloride.
4. The negative electrode material ZnCo of claim 1 for lithium ion battery2O4The preparation method of the nano-rod is characterized by comprising the following steps: in the step (2), the white precipitate is alternately cleaned for multiple times by adopting ethanol and distilled water, and is dried after being cleaned to obtain ZnCo2O4And (3) precursor.
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