CN111634962A - Lithium ion battery cathode material and preparation method thereof - Google Patents
Lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 61
- 239000010406 cathode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920000742 Cotton Polymers 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 14
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 12
- 238000007605 air drying Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims abstract description 3
- 230000008025 crystallization Effects 0.000 claims abstract description 3
- 230000008020 evaporation Effects 0.000 claims abstract description 3
- 239000007773 negative electrode material Substances 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012702 metal oxide precursor Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
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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
- C01G53/04—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The invention belongs to the technical field of lithium ion battery manufacturing, and particularly relates to a lithium ion battery cathode material and a preparation method thereof, wherein the lithium ion battery cathode material comprises the following steps: s1, preparing a nickel salt solution; s2, adding the biological template absorbent cotton into the completely dissolved nickel salt solution, soaking for 4-8 h, and then performing blast drying to obtain an absorbent cotton precursor; s3, calcining the absorbent cotton precursor in an air atmosphere to obtain pure-phase nickel oxide (NiO); s4, adding the pure-phase nickel oxide (NiO) serving as a precursor into a Graphene Oxide (GO) solution, heating and stirring at 40-75 ℃, and carrying out evaporation crystallization to obtain a NiO/GO composite material; and S5, carrying out forced air drying on the NiO/GO composite material to obtain the cathode material. The lithium ion battery cathode material prepared by the method has the advantages of low cost, simple synthesis method, strong operability, good electrochemical performance and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery manufacturing, and particularly relates to a lithium ion battery cathode material and a preparation method thereof.
Background
In recent years, with the rapid development of modern electronic industry, the energy crisis is becoming more serious, energy utilization and environmental protection are facing great challenges, and people have stronger and stronger demands for high-performance, light-weight and environment-friendly energy storage devices. As one of the most important energy storage and conversion devices, Lithium Ion Batteries (LIBs) have attracted much attention in academic research and commercial applications due to their outstanding advantages of high energy density, long cycle life, no memory effect, and environmental friendliness. In the lithium ion battery, due to the structural limitation of the cathode material, the theoretical capacity of the cathode material is far smaller than that of the anode material. Therefore, in order to increase the energy density of lithium ion batteries, the development of lithium ion battery negative electrode materials with higher theoretical capacity is continuously required. In the negative electrode material of the lithium ion battery, transition metal oxide (such as NiO, Fe)2O3，Fe3O4，Co3O4，Mn3O4，SnO2，MnO2Etc.) are desirable lithium ion battery negative electrode materials because they have high theoretical capacity and volumetric energy density. However, these negative electrode materials result in rapid capacity fade and poor cycling stability during cycling due to poor electron conductivity and large volume changes. To alleviate the problems faced by transition metal oxides, an effective approach is to synthesize nanostructures of different morphologiesThe storage capacity, the cycle life and the rate capability of the lithium ion battery are improved by compounding various carbon-based materials with the metal oxide.
When the method for synthesizing metal oxides with different morphologies is explored, methods such as electrostatic spinning, a hydrothermal method, a coprecipitation method and a pyrolysis method are used for synthesizing the metal oxides, but the synthesis method is relatively complex. Recently, the novel biological template method has been widely paid attention to by people because of its abundant resources, low cost, reproducibility, simple synthesis method, and unique pore structure in the long-term evolution process of biomass. And such pore structure materials are being increasingly applied in the negative electrode materials of lithium ion batteries. When various carbon-based materials are compounded with metal oxides, graphene is expected to replace traditional carbon materials in many fields due to the advantages of large specific surface area, unique mechanical properties, high electronic conductivity and the like. As a precursor of graphene, Graphene Oxide (GO) has a higher lithium storage capacity than graphite, and is also very good in chemical stability and dispersibility in water, in addition to inheriting the advantages of graphene. Meanwhile, the preparation of GO is simple and feasible, and the cost is lower than that of graphene, because reduction treatment is not needed. In addition, the presence of various oxygen-containing groups (mainly epoxy and hydroxyl groups) in GO allows the surface of GO to have many active sites available for immobilization of various active materials. However, relatively few reports have been made on the use of GO as a material for LIBs negative electrodes.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a lithium ion battery cathode material and a preparation method thereof, and aims to solve the problems of complex synthesis method, high cost, low energy density, poor cycle performance and poor environmental friendliness of the conventional lithium ion battery cathode material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a lithium ion battery negative electrode material comprises the following steps:
s1, preparing a nickel salt solution;
s2, adding the biological template absorbent cotton into the completely dissolved nickel salt solution, soaking for 4-8 hours, and performing forced air drying to obtain an absorbent cotton precursor;
s3, calcining the absorbent cotton precursor in an air atmosphere to obtain pure-phase nickel oxide (NiO);
s4, adding the pure-phase nickel oxide (NiO) serving as a precursor into a Graphene Oxide (GO) solution, heating and stirring at 40-75 ℃, and carrying out evaporation crystallization to obtain a NiO/GO composite material;
the step has the effect of improving the defect of poor electrochemical performance of pure-phase nickel oxide (NiO);
and S5, carrying out forced air drying on the NiO/GO composite material to obtain the cathode material.
Preferably, in step S1, the prepared nickel salt solution has a molar concentration of one of 0.1mol/L, 0.25mol/L, 0.5mol/L, or 0.75 mol/L.
Preferably, the nickel salt is one of nickel nitrate and nickel acetate.
Preferably, the mass ratio of the absorbent cotton to the nickel salt is 1 (3-4.5).
Preferably, the mass ratio of the absorbent cotton to the nickel salt is 1: 3.93.
Preferably, steps S2 and S4, conditions of forced air drying: the temperature is 60-80 ℃, and the time is 12-24 h.
Preferably, the calcination treatment is carried out by: calcining at 280-320 ℃ for 0.8-1.2 h, and then calcining at 400-700 ℃ for 1-3 h.
Preferably, the Graphene Oxide (GO) solution has a concentration of one of 2mg/mL, 4mg/mL, or 6 mg/mL.
Preferably, the negative electrode material is a nickel oxide-graphene oxide hollow tubular composite material, and the negative electrode material comprises a hollow tubular nickel oxide layer and a carbon coating layer.
The carbon coating layer is coated on a lithium ion battery cathode metal oxide (NiO) to form a composite hollow porous material, so that the structural stability of the lithium ion battery cathode material is further improved, the cycle stability of the lithium ion battery cathode material is improved, and the performance of the lithium ion battery cathode material is optimal.
Based on one general inventive concept, another object of the present invention is to provide a method for preparing the above negative electrode material for a lithium ion battery, including the steps of:
mixing the obtained negative electrode material with acetylene black and a binder PVDF according to the proportion of 7:2: 1; taking a proper amount of 1-methyl-2-pyrrolidone NMP as a solvent, and stirring for 5 hours to form uniform slurry; uniformly coating the slurry on a copper foil, putting the copper foil into a vacuum oven, and drying at 120 ℃ for 48 hours, wherein the mass of the active substance loaded on each electrode is about 2-3 mg/cm2。
In the invention, absorbent cotton with low cost is used as a raw material, nickel nitrate or nickel acetate is used as a nickel source, a biological template method is utilized to synthesize NiO with a pure-phase hollow tubular structure through simple soaking pyrolysis, in order to further improve the lithium storage performance, Graphene Oxide (GO) and NiO are compounded through a simple heating and stirring method to synthesize a NiO/GO composite material, and the NiO/GO composite material is dried to be used as a negative electrode material of a lithium ion battery, so that the electrochemical properties of the battery, such as storage capacity, cycle life, speed capacity and the like, are greatly improved.
Compared with the prior art, the invention has the following advantages and positive effects:
(1) the raw materials are rich, the cost is low, the synthesis process is simple, the operation is easy, and the mass synthesis is convenient;
(2) the prepared cathode material of the lithium ion battery has good cycle stability, rate capability and high theoretical capacity;
(3) the prepared cathode material has a unique hollow tubular structure, has the characteristics of easy shape control, large specific surface area and the like, has excellent electrochemical performance, and has great research and development values.
(4) The method for preparing the lithium ion battery cathode material mainly comprises the steps of obtaining pure-phase hollow tubular nickel oxide NiO, heating, stirring and evaporating to crystallize to obtain the hollow tubular NiO/GO composite material.
(5) The preparation method is simple and convenient, has strong operability, low cost and environmental friendliness, can be synthesized in a large scale, and finally prepares the lithium ion battery cathode material with unique appearance and good electrochemical performance.
Drawings
Fig. 1 is an XRD pattern of a product lithium ion battery anode material provided in example 3 of the present invention;
figure 2 TGA profile of a lithium ion battery anode material product provided in example 3 of the present invention;
fig. 3 is an SEM image of the negative electrode material for a lithium ion battery provided in example 3 of the present invention;
fig. 4 is a CV diagram of a lithium ion battery negative electrode material provided in example 3 of the present invention;
fig. 5 is a cycle performance diagram of the negative electrode material of the lithium ion battery provided in embodiment 3 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On one hand, the embodiment of the invention provides a lithium ion battery cathode material, which is a hollow tubular NiO/GO composite material;
on the other hand, the embodiment of the invention also provides a preparation method of the lithium ion battery cathode material, which is mainly characterized in that a nickel source and absorbent cotton are synthesized into a pure-phase metal oxide precursor by a biological template method, and the pure-phase metal oxide precursor is prepared by heating and stirring. The preparation method is simple and convenient, strong in operability, low in cost, environment-friendly and capable of being synthesized in a large scale, and the finally prepared lithium ion battery cathode material is unique in morphology and excellent in storage capacity, cycle performance, rate capability and other electrochemical properties.
The invention is described in more detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
The lithium ion battery cathode material comprises a hollow tubular NiO and a carbon coating layer coating the hollow tubular NiO; the preparation method of the lithium ion battery negative electrode material comprises the following steps:
s11: respectively preparing nickel nitrate solutions with the molar concentrations of 0.1mol/L, 0.25mol/L, 0.5mol/L or 0.75 mol/L;
s12: adding 1.7-2 g of absorbent cotton into the completely dissolved nickel nitrate solutions with different concentrations, soaking for 6h, and carrying out forced air drying at 70 ℃ for 18h to obtain an absorbent cotton precursor;
s13: calcining the absorbent cotton precursor in an air atmosphere to obtain pure-phase nickel oxide (NiO);
the calcining treatment process comprises the following steps: calcining at 300 ℃ for 1h, and then calcining at 600 ℃ for 2 h.
Example 2
The lithium ion battery cathode material comprises a hollow tubular NiO and a carbon coating layer coating the hollow tubular NiO; the preparation method of the lithium ion battery negative electrode material comprises the following steps:
s21: preparing a nickel acetate solution with the molar concentration of 0.25 mol/L;
s22: adding 1.8g of absorbent cotton into the completely dissolved nickel acetate solutions with different concentrations, soaking for 6h, and carrying out forced air drying at 70 ℃ for 18h to obtain an absorbent cotton precursor;
s23: calcining the absorbent cotton precursor in an air atmosphere to obtain pure-phase nickel oxide (NiO);
the calcining treatment process comprises the following steps: calcining at 300 ℃ for 1h, and then calcining at 600 ℃ for 2 h.
Example 3
The lithium ion battery cathode material comprises a hollow tubular NiO and a carbon coating layer coating the hollow tubular NiO; the preparation method of the lithium ion battery negative electrode material comprises the following steps:
s31: selecting the optimal pure phase NiO synthesized in the above embodiment 1 and embodiment 2 as a precursor;
s32: respectively adding the precursor pure-phase NiO into Graphene Oxide (GO) solutions with the concentrations of 2mg/mL, 4mg/mL and 6mg/mL, heating at 60 ℃, stirring, evaporating and crystallizing to obtain a NiO/GO composite material;
s33: and (3) carrying out forced air drying on the NiO/GO composite material for 18h at 70 ℃ to obtain the cathode material.
Test example
The lithium ion battery cathode material prepared in the embodiment 3 has the characteristics of good cycle stability and rate capability, high theoretical capacity and the like; the lithium ion battery negative electrode material of example 3 is now tested and verified for its relevant performance.
An XRD (X-ray diffraction) phase analysis diagram of the lithium ion battery composite material is shown in figure 1, the abscissa is an angle (2 theta), and the ordinate is strength, and the XRD phase analysis diagram shows that the lithium ion battery negative electrode material obtained in the embodiment 3 of the invention has good crystallinity and no impurity peak, so that the NiO/GO composite material can be successfully prepared by the preparation method, and the lithium ion battery negative electrode material obtained by the preparation method is pure and free of impurities and has a characteristic peak of GO.
The TGA of the lithium ion battery composite material is shown in fig. 2, and it can be seen from the TGA diagram that the weight loss of the lithium ion battery composite material comprises three stages, namely the weight loss of water, the weight loss of the oxygen-containing functional group of GO, and the carbon weight loss of GO, and the carbon content of the negative electrode material can also be seen.
An SEM topography analysis diagram of the lithium ion battery negative electrode material is shown in FIG. 3, and as can be seen from FIGS. 3a (2 μm) and 3b (200nm), the sample is a hollow tubular porous structure and is coated with carbon on the tubular structure.
The NiO/GO composite material obtained in the example 3 is mixed with acetylene black and PVDF binder according to the ratio of 7:2:1, and a proper amount of 1-methyl-2-pyrrolidone (NMP) is taken as a solvent and stirred for 5 hours to form uniform slurry. The slurry was uniformly coated on a copper foil and placed in a vacuum oven and dried at 120 ℃ for 48 h. The mass of the active substance loaded on each electrode is about 2-3 mg/cm2。
The assembly was carried out in a glove box under an Ar atmosphere using a CR2025 coin-type half cell. The active material prepared above was a working electrode, a lithium metal sheet was a counter electrode, and Celgrad 2400 was a separator. The electrolyte is 1mol/LLIPF6Dissolved in a mixture of Ethylene Carbonate (EC) and dimethyl carbon (DMC) (volume ratio 1: 1). After assembly, electrochemical performance was tested on CT2001 blue test system and CHI 600D.
The cyclic voltammogram obtained by this test procedure is shown in fig. 4, from which it can be seen that: the CV curve of the lithium ion battery anode material obtained in this example 3 shows that the corresponding oxidation-reduction process of the NiO/GO electrode can be expressed as follows:
the cycle performance obtained by this test procedure is shown in fig. 5, from which it can be seen that: the first discharge specific capacity of the pure-phase NiO of the lithium ion battery reaches 1046.70mAhg under the current density of 0.1A-1The first discharge specific capacity of the NiO/GO negative electrode material reaches 1315.88mAhg-1. Pure phase NiO started to fade in capacity after 50 cycles, but NiO/GO started to increase in capacity after 50 cycles. The capacity of pure phase nickel oxide NiO in 140 cycles is only 399.45mAhg left-1And the capacity of the NiO/GO electrode reaches 1042.59mAhg-1The lithium ion battery negative electrode material prepared by the preparation method of example 3 in the invention has good cycle performance.
The above embodiments are merely preferred embodiments of the present invention, and any simple modification, modification and substitution changes made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a lithium ion battery cathode material is characterized by comprising the following steps:
s1, preparing a nickel salt solution;
s2, adding the biological template absorbent cotton into the completely dissolved nickel salt solution, soaking for 4-8 hours, and performing forced air drying to obtain an absorbent cotton precursor;
s3, calcining the absorbent cotton precursor in an air atmosphere to obtain pure-phase nickel oxide (NiO);
s4, adding the pure-phase nickel oxide (NiO) serving as a precursor into a Graphene Oxide (GO) solution, heating and stirring at 40-75 ℃, and carrying out evaporation crystallization to obtain a NiO/GO composite material;
and S5, carrying out forced air drying on the NiO/GO composite material to obtain the cathode material.
2. The method of claim 1, wherein in step S1, the molar concentration of the prepared nickel salt solution is one of 0.1mol/L, 0.25mol/L, 0.5mol/L, and 0.75 mol/L.
3. The preparation method of the negative electrode material of the lithium ion battery according to claim 1 or 2, wherein the nickel salt is one of nickel nitrate and nickel acetate.
4. The preparation method of the lithium ion battery anode material according to claim 1, wherein the mass ratio of the absorbent cotton to the nickel salt is 1 (3-4.5).
5. The preparation method of the lithium ion battery anode material according to claim 4, wherein the mass ratio of the absorbent cotton to the nickel salt is 1: 3.93.
6. The method for preparing the negative electrode material of the lithium ion battery according to claim 1, wherein the air-blast drying conditions in steps S2 and S4 are as follows: the temperature is 60-80 ℃, and the time is 12-24 h.
7. The preparation method of the lithium ion battery anode material according to claim 1, wherein the calcining treatment comprises the following steps: calcining at 280-320 ℃ for 0.8-1.2 h, and then calcining at 400-700 ℃ for 1-3 h.
8. The method of claim 1, wherein the Graphene Oxide (GO) solution is at a concentration of one of 2mg/mL, 4mg/mL, or 6 mg/mL.
9. The lithium ion battery negative electrode material prepared by the preparation method of any one of claims 1 to 8, which is characterized in that: the cathode material is a nickel oxide-graphene oxide hollow tubular composite material, and comprises a hollow tubular nickel oxide layer and a carbon coating layer.
10. The application of the lithium ion battery cathode material prepared by the preparation method according to any one of claims 1 to 8 is characterized in that: mixing the obtained negative electrode material with acetylene black and a binder PVDF according to the proportion of 7:2: 1; taking a proper amount of 1-methyl-2-pyrrolidone NMP as a solvent, and stirring for 5 hours to form uniform slurry; uniformly coating the slurry on a copper foil, putting the copper foil into a vacuum oven, and drying at 120 ℃ for 48 hours, wherein the mass of the active substance loaded on each electrode is about 2-3 mg/cm2。
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| CN112436111A (en) * | 2020-10-26 | 2021-03-02 | 滨州双峰石墨密封材料有限公司 | Preparation method and application of graphene modified nickel oxide nanocomposite |
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| MEI MA ET AL.: ""Cladding transition metal oxide particles with graphene oxide sheets: an efficient protocol to improve their structural stability and lithium ion diffusion rate"", 《JOURNAL OF SOLID STATE ELECTROCHEMISTRY 》 * |
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| CN112436111A (en) * | 2020-10-26 | 2021-03-02 | 滨州双峰石墨密封材料有限公司 | Preparation method and application of graphene modified nickel oxide nanocomposite |
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