CN110137450B - Preparation method of chromium titanium-based lithium ion battery composite material - Google Patents

Preparation method of chromium titanium-based lithium ion battery composite material Download PDF

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CN110137450B
CN110137450B CN201910338972.4A CN201910338972A CN110137450B CN 110137450 B CN110137450 B CN 110137450B CN 201910338972 A CN201910338972 A CN 201910338972A CN 110137450 B CN110137450 B CN 110137450B
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CN110137450A (en
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韩明凯
姚汪兵
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Nanjing Guoxuan Battery Co Ltd
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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a preparation method of a chromium titanium-based lithium ion battery composite material, which comprises the following steps: s1, dissolving a titanium source and a chromium source in an aqueous solution of absolute ethyl alcohol, adding an aqueous solution of ethyl alcohol containing a lithium source, stirring, then adding an aqueous solution containing nickel nitrate and sodium molybdate, stirring, reacting for 24-26h at the temperature of 140-; s2, drying the precursor, presintering, cooling, ball-milling, sieving, sintering and cooling to obtain LiCrTiO4‑aNiMoO4A material; s3, preparing LiCrTiO4‑aNiMoO4Dissolving the material in deionized water, performing ultrasonic dispersion, adding a surfactant, stirring, then adding a pyrrole monomer, hydrochloric acid and an ammonium persulfate aqueous solution, stirring, filtering and drying to obtain the chromium-titanium-based lithium ion battery composite material.

Description

Preparation method of chromium titanium-based lithium ion battery composite material
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a chromium titanium-based lithium ion battery composite material.
Background
With the reduction of non-renewable energy and the aggravation of environmental pollution, the development of novel energy and environment-friendly energy has important significance. The development of various electronic devices, electric vehicles, and hybrid vehicles has put higher demands on lithium ion batteries for supplying energy to the electronic devices. Lithium ion batteries have high output voltage, high energy density and power density, long cycle life, and the like, and are recognized as the most promising power batteries.
At present, various lithium-embedded carbon/graphite materials are mostly adopted as negative electrode materials of commercial lithium ion batteries, however, the lithium-embedded potential (0-0.26V) of the carbon material is very close to the deposition potential of metallic lithium, when the batteries are overcharged, the metallic lithium may be separated out on the surface of a carbon electrode to form lithium dendrites, and the dendrites further grow and may pierce through a diaphragm to cause the connection of a positive electrode and a negative electrode, thereby causing short circuit; in addition, the carbon material has low first charge-discharge efficiency, acts with electrolyte, has obvious voltage hysteresis phenomenon and is high in powerLow current charge and discharge capacity, and the like. Compared with graphite, spinel lithium titanate Li4Ti5O12As a negative electrode material, the lithium ion battery has a high charge-discharge platform (1.55V), the formation of lithium dendrites in electrochemical reaction is avoided, and the safety of the material in an electrochemical process in which Li is used is ensured4Ti5O12Hardly undergoes changes in volume, which makes it one of the most promising anode materials. And the 3d orbit of Ti in lithium titanate is empty orbit, and the band gap energy is about 2V, so that Li4Ti5O12The negative electrode material becomes an insulator, severely limiting Li4Ti5O12High rate capability of the material. For Li4Ti5O12Carrying out cation doping modification when 3 Cr3+By replacement of one Li+And 2 of Ti4+Post-production of another stoichiometric spinel material Li3Cr3Ti3O12(LiCrTiO4)。LiCrTiO4The cathode material also has a spinel structure, has a stable charge-discharge platform (about 1.6V) and a theoretical capacity of 157mAh g-1And the electrochemical performance is excellent. Oxide electrode material NiMoO4Has an electrical conductivity of 10-6S·cm-1The polypyrrole can be directly synthesized in a doped state in a conductive polymer by a simple process, has high conductivity (P type) and the conductivity of 10-100S·cm-1Within the range, the lithium ion battery has very high charge density, better charge-discharge rate performance and good thermal stability at the temperature of up to 250 ℃, and has an important effect on improving the conductivity of the lithium ion battery.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of a chromium titanium-based lithium ion battery composite material, the particle size of the obtained material is small, the distribution is uniform, the crystallinity is high, the preparation cost of the material is reduced, and the electrochemical performance of the material is improved.
The invention provides a preparation method of a chromium titanium-based lithium ion battery composite material, which comprises the following steps:
s1, dissolving a titanium source and a chromium source in an aqueous solution of absolute ethyl alcohol, adding an aqueous solution of ethyl alcohol containing a lithium source, stirring, then adding an aqueous solution containing nickel nitrate and sodium molybdate, stirring, reacting for 24-26h at the temperature of 140-;
s2, drying the precursor, presintering, cooling, ball-milling, sieving, sintering and cooling to obtain LiCrTiO4-aNiMoO4A material;
s3 preparation of LiCrTiO4-aNiMoO4Dissolving the material in deionized water, performing ultrasonic dispersion, adding a surfactant, stirring, then adding a pyrrole monomer, hydrochloric acid and an ammonium persulfate aqueous solution, stirring, filtering and drying to obtain the chromium-titanium-based lithium ion battery composite material.
Preferably, in S1, dissolving a titanium source and a chromium source in an aqueous solution of absolute ethyl alcohol, adding the aqueous solution of ethyl alcohol containing a lithium source under the condition of stirring, magnetically stirring for 1-1.5h, then adding an aqueous solution containing nickel nitrate and sodium molybdate, magnetically stirring for 1-1.5h, reacting at 140-; wherein the molar ratio of the lithium source to the chromium source to the titanium source is 1-1.5:0.8-1.2:0.8-1.2, and the molar ratio of the nickel nitrate to the sodium molybdate is 1:1.
Preferably, the molar ratio of the lithium source, the chromium source and the titanium source is 1.25:1: 1.
Preferably, in S1, the titanium source is one of tetrabutyl titanate and tetrapropyl titanate, the chromium source is one of chromium nitrate nonahydrate and chromium acetate, and the lithium source is one of lithium hydroxide monohydrate, lithium nitrate and lithium acetate dihydrate.
Preferably, in S2, the precursor is placed at 80-85 ℃ for drying, ground, pre-sintered at 600-630 ℃ for 5.5-6h, cooled to room temperature, ball-milled for 2.5-3h, sieved, sintered at 800-840 ℃ for 11-12h, and cooled to room temperature to obtain LiCrTiO4-aNiMoO4A material.
Preferably, in S3, LiCrTiO4-aNiMoO4Dissolving the material in deionized water, performing ultrasonic dispersion for 3-3.5h, adding a surfactant, stirring for 12-13h, and then dropwise adding pyrrole monomer, hydrochloric acid with the concentration of 0.5-1.5mol/L and persulfuric acid with the concentration of 3-5g/LAnd stirring the ammonium water solution in an ice-water bath for 2 to 2.5 hours, filtering, and drying at the temperature of between 50 and 55 ℃ to obtain the chromium-titanium-based lithium ion battery composite material.
Preferably, in S3, LiCrTiO4-aNiMoO4The mass ratio of the materials to the surfactant is 40-60: 0.8-1.2.
Preferably, in S3, LiCrTiO4-aNiMoO4The mass-volume ratio (kg/ml) of the material to the pyrrole monomer is 8-12: 0.8-1.2.
Preferably, in S3, the volume ratio of the pyrrole monomer, the hydrochloric acid and the ammonium persulfate aqueous solution is 0.03-0.07:0.45-0.55: 36-44.
Preferably, in S3, the surfactant is one of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, and cetyltrimethyl ammonium bromide.
Preferably, in S3, the composite material is a submicron composite material of the LiCrTiO4-aNiMoO4@ PPy, wherein a is more than or equal to 0.083 and less than or equal to 0.333.
The invention has the beneficial effects that:
(1) the material particles synthesized by the method have small particle size, uniform distribution, good dispersibility and high crystallinity; wherein, polypyrrole (PPy) plays a skeleton supporting role in the composite material, LiCrTiO4-aNiMoO4Is filled in a three-dimensional cavity constructed by polypyrrole (PPy) to perfect LiCrTiO4-aNiMoO4Gaps among the particles further enable the whole composite material to be uniformly and compactly dispersed, and the stability and high conductivity of the electrode structure are kept.
(2) The chromium-titanium-based lithium ion battery composite material has good wide potential window reversible capacity, excellent rate capability and stable cycle life, so that the material has high practical use value and can effectively meet the practical requirements of various applications of lithium ion batteries.
(3) The chromium-titanium-based lithium ion battery composite material has higher discharge capacity and rapid charge and discharge performance, improves the energy density and the power density of the lithium ion battery, and has cheap and easily obtained raw materials.
(4) The invention reduces the usage amount of lithium element, thereby reducing the cost.
Drawings
FIG. 1 is an XRD pattern of a composite material of a TiNi-based Li-ion battery obtained in example 1 of the present invention;
FIG. 2 is an SEM image of a TiNi-based lithium ion battery composite material obtained in example 1 of the present invention;
FIG. 3 is a charge-discharge curve diagram of the chromium titanium-based lithium ion battery composite material obtained in example 1 of the present invention at different rates;
fig. 4 is a cycle curve diagram of the composite material of the chromium titanium-based lithium ion battery obtained in example 1 of the present invention at a rate of 5C.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The invention provides a preparation method of a chromium titanium-based lithium ion battery composite material, which comprises the following steps:
s1, weighing 12mol of tetrabutyl titanate and 12mol of chromium nitrate nonahydrate, dissolving the tetrabutyl titanate and the 12mol of chromium nitrate nonahydrate in an aqueous solution of absolute ethyl alcohol, adding an aqueous solution of ethyl alcohol containing 15mol of lithium hydroxide monohydrate under the stirring condition, magnetically stirring for 1h, then adding an aqueous solution containing 2mol of nickel nitrate and 2mol of sodium molybdate, magnetically stirring for 1h, transferring the mixed solution into a stainless steel polytetrafluoroethylene reaction kettle, putting the stainless steel polytetrafluoroethylene reaction kettle into an oven to react for 24h at 160 ℃, cooling to room temperature, and filtering the mixed solution in the reaction kettle to obtain a precursor;
s2, placing the precursor in an oven, drying at 80 ℃, pre-burning in a muffle furnace at 600 ℃ for 6h after grinding, cooling to room temperature, ball-milling in a ball mill for 3h, sieving, placing in the muffle furnace, sintering at 800 ℃ for 12h, and cooling to room temperature to obtain LiCrTiO4-0.167NiMoO4 material;
s3, dissolving 500mg LiCrTiO4-0.167NiMoO4 material in deionized water, ultrasonically dispersing for 3h, adding 10mg sodium dodecyl sulfate, stirring for 12h, dropwise adding 0.05mL pyrrole monomer, 0.5mL hydrochloric acid with the concentration of 1mol/L and 40mL hydrochloric acid with the concentration of 4 g.L < -1 > into the suspensionStirring the ammonium persulfate aqueous solution in an ice-water bath for 2 hours, filtering, and drying in vacuum at 50 ℃ to obtain the chromium-titanium-based lithium ion battery composite material; wherein the chromium titanium-based lithium ion battery composite material is a submicron chromium titanium-based lithium ion battery composite material with a chemical formula of LiCrTiO4-0.167NiMoO4@PPy。
The performance of the chromium titanium-based lithium ion battery composite material obtained in the embodiment 1 of the invention is detected to obtain a figure 1, a figure 2, a figure 3 and a figure 4; wherein, fig. 1 is an XRD chart of the composite material of the chromium titanium based lithium ion battery obtained in example 1 of the present invention; FIG. 2 is an SEM image of a TiNi-based lithium ion battery composite material obtained in example 1 of the present invention; FIG. 3 is a charge-discharge curve diagram of the chromium titanium-based lithium ion battery composite material obtained in example 1 of the present invention at different rates; fig. 4 is a cycle curve diagram of the composite material of the chromium titanium-based lithium ion battery obtained in example 1 of the present invention at a rate of 5C.
As can be seen from fig. 1, the obtained chromium titanium based lithium ion battery composite material has the same spinel structure as LiCrTiO 4;
as can be seen from FIG. 2, the particle size of the obtained chromium-titanium-based lithium ion battery composite material is about 100nm, and the distribution is uniform and compact;
as shown in FIG. 3, the obtained composite material of chromium titanium-based lithium ion battery is used as an electrode material, and is assembled into an experimental button type lithium ion battery in a glove box filled with argon, and charge and discharge cycles are carried out between 1V and 2.5V at the multiplying power of 0.5C, 1C, 3C, 5C and 0.5C, and as can be seen from FIG. 3, the initial charge capacities are 127.7, 107.6, 103.3, 92.4 and 111.6mAh g-1The capacity recovered to 0.5C multiplying power after charging and discharging for 20 times is 110.5mAh g-1It has good discharge capacity;
as shown in FIG. 4, the first discharge capacity was 117.5mAh · g when the cycle test was performed at a rate of 5C-1And the capacity after 100 cycles is 95.6mAh g-1It exhibits excellent rapid charge and discharge properties and cycle stability.
Example 2
The invention provides a preparation method of a chromium titanium-based lithium ion battery composite material, which comprises the following steps:
s1, dissolving a titanium source and a chromium source in an aqueous solution of absolute ethyl alcohol, adding an aqueous solution of ethyl alcohol containing a lithium source, stirring, then adding an aqueous solution containing nickel nitrate and sodium molybdate, stirring, reacting for 26 hours at 140 ℃, cooling, and filtering to obtain a precursor;
s2, drying the precursor, presintering, cooling, ball-milling, sieving, sintering and cooling to obtain LiCrTiO4-aNiMoO4A material;
s3 preparation of LiCrTiO4-aNiMoO4Dissolving the material in deionized water, performing ultrasonic dispersion, adding a surfactant, stirring, then adding a pyrrole monomer, hydrochloric acid and an ammonium persulfate aqueous solution, stirring, filtering and drying to obtain the chromium-titanium-based lithium ion battery composite material.
Example 3
The invention provides a preparation method of a chromium titanium-based lithium ion battery composite material, which comprises the following steps:
s1, dissolving tetrapropyl titanate and chromium acetate in an aqueous solution of absolute ethyl alcohol, adding the aqueous solution of ethyl alcohol containing lithium acetate dihydrate under the condition of stirring, magnetically stirring for 1.5h, then adding the aqueous solution containing nickel nitrate and sodium molybdate, magnetically stirring for 1.5h, reacting for 26h at 140 ℃, cooling to room temperature, and filtering to obtain a precursor; wherein the molar ratio of lithium acetate dihydrate, chromium acetate and tetrapropyl titanate is 1:1:1, and the molar ratio of nickel nitrate and sodium molybdate is 1: 1;
s2, drying the precursor at 85 ℃, grinding, presintering at 630 ℃ for 5.5h, cooling to room temperature, ball-milling for 2.5h, sieving, sintering at 840 ℃ for 11h, and cooling to room temperature to obtain LiCrTiO4-0.083NiMoO4A material;
s3 preparation of LiCrTiO4-0.083NiMoO4Dissolving the material in deionized water, performing ultrasonic dispersion for 3.5h, adding sodium dodecyl benzene sulfonate, stirring for 13h, then dropwise adding pyrrole monomer, hydrochloric acid with the concentration of 0.5mol/L and ammonium persulfate aqueous solution with the concentration of 3g/L, stirring for 2.5h in an ice-water bath, filtering, and drying at 55 ℃ to obtain the submicron chromium titanium-based lithium ion battery composite material; wherein, LiCrTiO4-0.083NiMoO4Material, sodium dodecylbenzenesulfonateThe mass ratio of the LiCrTiO to the LiCrTiO is 40:14-0.083NiMoO4The mass volume ratio (kg/ml) of the material to the pyrrole monomer is 10:0.8, and the volume ratio of the pyrrole monomer, the hydrochloric acid and the ammonium persulfate aqueous solution is 0.08:0.55: 44.
Example 4
The invention provides a preparation method of a chromium titanium-based lithium ion battery composite material, which comprises the following steps:
s1, dissolving tetrabutyl titanate and chromium nitrate nonahydrate in an aqueous solution of absolute ethyl alcohol, adding an aqueous solution of ethyl alcohol containing lithium nitrate under the condition of stirring, magnetically stirring for 1.2h, then adding an aqueous solution containing nickel nitrate and sodium molybdate, magnetically stirring for 1.2h, reacting for 24h at 180 ℃, cooling to room temperature, and filtering to obtain a precursor; wherein the molar ratio of the lithium nitrate to the chromium nitrate nonahydrate to the tetrabutyl titanate is 1.2:1:1, and the molar ratio of the nickel nitrate to the sodium molybdate is 1: 1;
s2, drying the precursor at 82 ℃, grinding, presintering at 615 ℃ for 5.8h, cooling to room temperature, ball-milling for 2.6h, sieving, sintering at 830 ℃ for 11.2h, and cooling to room temperature to obtain LiCrTiO4-0.333NiMoO4A material;
s3 preparation of LiCrTiO4-0.333NiMoO4Dissolving the material in deionized water, performing ultrasonic dispersion for 3.4h, adding hexadecyl trimethyl ammonium bromide, stirring for 12.6h, then dropwise adding pyrrole monomer, hydrochloric acid with the concentration of 1.2mol/L and an ammonium persulfate aqueous solution with the concentration of 4.5g/L, stirring for 2.2h in an ice water bath, filtering, and drying at 52 ℃ to obtain the submicron chromium titanium-based lithium ion battery composite material; wherein, LiCrTiO4-0.333NiMoO4The mass ratio of the material to the hexadecyl trimethyl ammonium bromide is 40:1.2, and LiCrTiO4-0.333NiMoO4The mass volume ratio (kg/ml) of the material to the pyrrole monomer is 12:1, and the volume ratio of the pyrrole monomer, the hydrochloric acid and the ammonium persulfate aqueous solution is 0.06:0.48: 40.
Example 5
The invention provides a preparation method of a chromium titanium-based lithium ion battery composite material, which comprises the following steps:
s1, dissolving tetrabutyl titanate and chromium acetate in an aqueous solution of absolute ethyl alcohol, adding the aqueous solution of ethyl alcohol containing lithium acetate dihydrate under the condition of stirring, magnetically stirring for 1.4h, then adding the aqueous solution containing nickel nitrate and sodium molybdate, magnetically stirring for 1.4h, reacting for 24.5h at 165 ℃, cooling to room temperature, and filtering to obtain a precursor; wherein the molar ratio of the lithium nitrate to the chromium nitrate nonahydrate to the tetrabutyl titanate is 1.4:1.1:1.1, and the molar ratio of the nickel nitrate to the sodium molybdate is 1: 1;
s2, drying the precursor at 84 ℃, grinding, presintering at 625 ℃ for 5.6h, cooling to room temperature, ball-milling for 2.8h, sieving, sintering at 825 ℃ for 11.2h, cooling to room temperature to obtain LiCrTiO4-0.215NiMoO4A material;
s3 preparation of LiCrTiO4-0.215NiMoO4Dissolving the material in deionized water, performing ultrasonic dispersion for 3.3h, adding hexadecyl trimethyl ammonium bromide, stirring for 12.4h, then dropwise adding pyrrole monomer, hydrochloric acid with the concentration of 0.8mol/L and ammonium persulfate aqueous solution with the concentration of 3.5g/L, stirring for 2.4h in an ice water bath, filtering, and drying at 53 ℃ to obtain the submicron chromium titanium-based lithium ion battery composite material; wherein, LiCrTiO4-0.215NiMoO4The mass ratio of the material to the hexadecyl trimethyl ammonium bromide is 50:1, and LiCrTiO4-0.215NiMoO4The mass volume ratio (kg/ml) of the material to the pyrrole monomer is 9:0.8, and the volume ratio of the pyrrole monomer, the hydrochloric acid and the ammonium persulfate aqueous solution is 0.05:0.5: 40.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. The preparation method of the chromium-titanium-based lithium ion battery composite material is characterized by comprising the following steps of:
s1, dissolving a titanium source and a chromium source in an aqueous solution of absolute ethyl alcohol, adding an aqueous solution of ethyl alcohol containing a lithium source, stirring, then adding an aqueous solution containing nickel nitrate and sodium molybdate, stirring, reacting for 24-26h at the temperature of 140-;
s2, drying the precursor, presintering, cooling, ball-milling, sieving, sintering and cooling to obtain LiCrTiO4-aNiMoO4A material;
s3 preparation of LiCrTiO4-aNiMoO4Dissolving the material in deionized water, performing ultrasonic dispersion, adding a surfactant, stirring, then adding a pyrrole monomer, hydrochloric acid and an ammonium persulfate aqueous solution, stirring, filtering and drying to obtain the chromium-titanium-based lithium ion battery composite material.
2. The method for preparing the TiNi-based Li-ion battery composite material as claimed in claim 1, wherein in S1, dissolving Ti source and Cr source in the aqueous solution of absolute ethanol, adding the aqueous solution of ethanol containing Li source under stirring, magnetically stirring for 1-1.5h, adding the aqueous solution containing Ni nitrate and sodium molybdate, magnetically stirring for 1-1.5h, reacting at 140-180 ℃ for 24-26h, cooling to room temperature, and filtering to obtain the precursor; wherein the molar ratio of the lithium source to the chromium source to the titanium source is 1-1.5:0.8-1.2:0.8-1.2, and the molar ratio of the nickel nitrate to the sodium molybdate is 1: 1; the molar ratio of the lithium source, the chromium source and the titanium source is 1.25:1: 1.
3. The method for preparing the TiNi-based lithium ion battery composite material of claim 1 or 2, wherein in S1, the Ti source is one of tetrabutyl titanate and tetrapropyl titanate, the Cr source is one of chromium nitrate nonahydrate and chromium acetate, and the Li source is one of lithium hydroxide monohydrate, lithium nitrate and lithium acetate dihydrate.
4. The method for preparing the TiNi-based lithium ion battery composite material as claimed in claim 1, wherein in S2, the precursor is dried at 80-85 ℃, pre-sintered at 600-630 ℃ for 5.5-6h after being ground, cooled to room temperature, ball-milled for 2.5-3h, sieved, sintered at 800-840 ℃ for 11-12h, and cooled to room temperature to obtain LiCrTiO4-aNiMoO4A material.
5. The method of claim 1, wherein in step S3 LiCrTiO is added4-aNiMoO4Dissolving the material in deionized water, performing ultrasonic dispersion for 3-3.5h, adding a surfactant, stirring for 12-13h, then dropwise adding pyrrole monomer, hydrochloric acid with the concentration of 0.5-1.5mol/L and an ammonium persulfate aqueous solution with the concentration of 3-5g/L, stirring for 2-2.5h in an ice water bath, filtering, and drying at 50-55 ℃ to obtain the chromium titanium-based lithium ion battery composite material.
6. The method of claim 1, wherein in S3 LiCrTiO is used to prepare the composite material for Li-Ti-Cr-based battery4-aNiMoO4The mass ratio of the materials to the surfactant is 40-60: 0.8-1.2.
7. The method of claim 1, wherein in S3 LiCrTiO is used to prepare the composite material for Li-Ti-Cr-based battery4-aNiMoO4The mass-volume ratio (kg/ml) of the material to the pyrrole monomer is 8-12: 0.8-1.2.
8. The method for preparing the TiNi-based lithium ion battery composite material of claim 1, wherein in S3, the volume ratio of the pyrrole monomer, the hydrochloric acid and the ammonium persulfate aqueous solution is 0.03-0.07:0.45-0.55: 36-44.
9. The method of claim 1, wherein in S3, the surfactant is one of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, and cetyl trimethyl ammonium bromide.
10. The method of claim 1, wherein in step S3, the composite material is a submicron composite material of LiCrTiO4-aNiMoO4@ PPy, wherein a is more than or equal to 0.083 and less than or equal to 0.333.
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