CN111180709B - Carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and preparation method thereof - Google Patents

Carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and preparation method thereof Download PDF

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CN111180709B
CN111180709B CN202010044910.5A CN202010044910A CN111180709B CN 111180709 B CN111180709 B CN 111180709B CN 202010044910 A CN202010044910 A CN 202010044910A CN 111180709 B CN111180709 B CN 111180709B
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姚耀春
张克宇
杨斌
米如中
马文会
杨桂玲
梁风
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Kunming University of Science and Technology
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract

The invention discloses a carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and a preparation method thereof, belonging to the technical field of lithium ion battery negative electrode materials; the invention relates to a ferrous oxalate complex Fe (C) with positive charges on the surface of a carbon nano tube treated by strong cationic polyelectrolyte and negative charges in the preparation process of ferrous oxalate2O4)2 ‑2Electrostatic attraction and self-assembly to form Fe (C) doped with carbon nanotube2O4)2 ‑2MWCNTs polymer, reaction of the obtained polymer with soluble copper salts to form Fe x Cu 1‑ x C2O4/MWCNTs·yH2O precursor; sintering under the inert atmosphere condition by utilizing the difference of thermodynamic properties among different transition metal oxalates, and decomposing a precursor in situ to obtain a carbon nano tube and metal copper co-doped ferrous oxalate composite material; the invention overcomes the problems of low conductivity, low lithium ion migration rate, high first irreversible capacity, poor cycle performance and the like of the ferrous oxalate negative electrode material in the prior art due to the self reason.

Description

Carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and preparation method thereof
Technical Field
The invention relates to a carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and a preparation method thereof, belonging to the technical field of lithium ion battery negative electrode materials.
Background
In recent years, lithium ion batteries have high volumetric energy density and power density, become small portable devices, and are one of the first power sources of large hybrid power machines, and in consideration of the requirements of electric vehicles on the driving mileage and energy density, the lithium ion batteries still face great challenges in performance, cost and safety. Up to now, graphite-based materials still dominate lithium ion battery negative electrode materials. However, its low specific charge-discharge capacity severely limits its further development. Therefore, the development of a novel negative electrode material with high energy density, low cost and safe use has become a hot spot of battery material research in recent years.
At present, the research on the negative electrode material of the lithium ion battery is mainly divided into the following steps according to the lithium storage mechanism of the material: insert type (graphite, TiO)2、Li4Ti5O12) Alloying type (Si, Sn, Al, etc.) and conversion reaction type (Fe)2O3NiO, CoO, etc.). Compared with other alternative materials, the metal oxalate based on the conversion reaction has the advantages of high reversible capacity, excellent cycle performance, abundant resources, environmental friendliness, high safety and the like. However, due to its low electron conductivity, Li+Slow diffusion rates lead to higher first irreversible capacity, poorer rate performance. Thus, the electron conductivity and Li of the material are improved+The diffusion rate becomes a research hotspot of researchers at home and abroad in the aspect of improving the performance of the transition metal oxalate. The following two classes can be roughly classified according to the modification mechanism: (1) and (3) designing a morphology structure: shortening Li by controlling the diversity (cocoon, rod, nanowire, three-dimensional sphere, etc.) and structural composition of the material particle morphology+The insertion/extraction distance of (a) increases a stable diffusion channel; (2) doping modification: in one aspect, the cation sites in the oxalate lattice are doped with metal ions (Co, Mn, Cu, etc.) to improve the material electronic conductivity and Li+A diffusion rate; on the other hand, carbon materials such as graphene are added into oxalate materials to prepare oxalate/graphene (MC)2O4Mg, M = Fe, Mn, Cu, Co, Zn, etc.) composite material, which is a composite materialNot only improves the electronic conductivity of the whole material, but also provides enough gaps for the electrolyte to permeate into the electrode. The doping modification research is mainly single doping, so that the problems of unobvious improvement of material performance and the like are easily caused.
Disclosure of Invention
Aiming at the problems of low conductivity, low lithium ion migration rate, high first irreversible capacity, poor cycle performance and the like of the ferrous oxalate negative electrode material caused by the self reason; the invention provides a preparation method of a carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite cathode material, which is characterized in that the carbon nano tube, metal copper and rod-shaped ferrous oxalate are compounded by adopting a method of electrostatic self-assembly and in-situ growth, on one hand, the addition of the carbon nano tube provides more and more stable diffusion channels for the migration of lithium ions among material particles, and on the other hand, the introduction of the metal copper can obviously improve the conductivity of an electrode material, thereby improving the electrochemical reaction capability.
The invention is realized by a simple electrostatic self-assembly and in-situ growth method, soluble ferrous salt and oxalic acid are used as raw materials, and a ferrous oxalate complex with negative charges is synthesized at room temperature; then treating the carbon nano tube by strong cationic polyelectrolyte to make the carbon nano tube have positive charges; mixing the two materials with different charges, carrying out electrostatic self-assembly to obtain a carbon nano tube composite ferrous oxalate complex, adding a proper amount of soluble copper salt, moving into a reaction kettle for low-temperature treatment, and further optimizing the morphology structure of a precursor; and washing and drying the precursor treated at low temperature, and finally carrying out low-temperature heat treatment to obtain the carbon nano tube and metal copper co-doped ferrous weed lithium ion battery composite negative electrode material.
The preparation method of the carbon nanotube and metal copper co-doped ferrous weed acid lithium ion battery composite negative electrode material comprises the following steps:
(1) sequentially adding a surfactant cetyl trimethyl ammonium bromide and a carbon nano tube into a mixed solution of ethanol and deionized water, wherein the mass ratio of the surfactant to the carbon nano tube is 1: 5-1: 20, carrying out ultrasonic treatment at normal temperature for 3-5 h, dropwise adding a polydiallyldimethyl ammonium chloride aqueous solution with the concentration of 0.2-10 mg/mL, wherein the mass ratio of the carbon nano tube to the polydiallyldimethyl ammonium chloride is 1: 5-1: 20, fully stirring and mixing for 1-3 h, carrying out centrifugal separation, washing with deionized water to remove physically adsorbed polydiallyldimethyl ammonium chloride, then placing in an inert gas atmosphere, and drying at 40-60 ℃ to obtain a carbon nano tube material with positive charges;
(2) sequentially adding soluble ferrous salt, oxalic acid and ascorbic acid into a mixed solution of ethanol and deionized water, and stirring for 24-52 hours at normal temperature to obtain a ferrous oxalate complex solution, wherein the molar ratio of the soluble ferrous salt to the oxalic acid is 1: 5-1: 10;
(3) adding the carbon nanotube material with positive charges in the step (1) into the ferrous oxalate complex solution in the step (2), stirring for 30min at normal temperature, slowly adding soluble copper salt into the mixed solution, wherein the molar ratio of the soluble copper salt to the soluble ferrous salt is 1: 30-1: 9, continuously stirring and mixing for 1-2 h, transferring into a high-temperature high-pressure reaction kettle, reacting for 6-24 h at 60-150 ℃, filtering, washing and drying after the reaction is finished and natural cooling to obtain Fe x Cu 1-x C2O4/MWCNTs·yH2O precursor (0)<x<1，0<y<2）；
(4) Under the atmosphere of argon or nitrogen, Fe obtained in the step (3) x Cu 1-x C2O4/MWCNTs·yH2And (3) placing the O precursor in a vacuum tube furnace, and sintering at 200-300 ℃ for 1-6 h to obtain the carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material.
The mixed solution of the ethanol and the deionized water in the steps (1) and (2) is prepared by mixing the ethanol and the deionized water according to the volume ratio of 1: 1.
In the step (2), the soluble ferrous salt is one or more of ferrous chloride, ferrous sulfate, ferrous nitrate and ferrous acetate.
In the step (3), the soluble copper salt is one or more of copper chloride, copper sulfate, copper nitrate and copper acetate.
Fe in the step (3) x Cu 1-x C2O4/MWCNTs·yH2The precursor of the oxygen is O,xthe range is 0-1;ythe range is 0 to 2.
The composite cathode material of the lithium ion battery with the co-doped ferrous weed acid of the carbon nano tube and the metal copper is prepared by the method of electrostatic self-assembly and in-situ growth, and more stable diffusion channels are provided for the migration of lithium ions among material particles by utilizing the excellent channel structure of the carbon nano tube; the high conductivity of the metal copper is utilized to improve the conductivity of the material, thereby improving the electrochemical conversion reaction capability. In addition, the stable crystal and structural characteristics of the carbon nano tube also provide a better structural framework for the active material, so that the cycle stability of the composite material is obviously improved.
Drawings
Fig. 1 is a TG thermogravimetric curve of the carbon nanotube and metal copper co-doped ferrous oxalate composite material prepared in example 1 (a) and example 2 (b) of the present invention;
FIG. 2 is an X-ray diffraction diagram of a carbon nanotube and copper metal co-doped ferrous oxalate composite material prepared in example 2 of the present invention;
fig. 3 is a scanning electron microscope (a) and a projection electron microscope (b) of the carbon nanotube and copper-co-doped ferrous oxalate composite material prepared in example 1 of the present invention;
fig. 4 is a graph showing charge and discharge rates and cycles of the carbon nanotube and copper metal co-doped ferrous oxalate composite material prepared in examples 1, 2 and 3 of the present invention, wherein a is the graph of example 1, b is the graph of example 2, and c is the graph of example 3.
Detailed Description
The invention is described in more detail below with reference to the figures and examples, without limiting the scope of the invention.
Example 1: the preparation method of the carbon nanotube and metal copper co-doped ferrous weed acid lithium ion battery composite negative electrode material comprises the following steps:
(1) sequentially adding a surfactant cetyl trimethyl ammonium bromide and a carbon nano tube into a mixed solution (volume ratio is 1: 1) of ethanol and deionized water, wherein the mass ratio of the surfactant to the carbon nano tube is 1:10, performing ultrasonic treatment at normal temperature for 3 hours, dropwise adding a polydiallyldimethyl ammonium chloride aqueous solution with the concentration of 0.5mg/mL, wherein the mass ratio of the carbon nano tube to the polydiallyldimethyl ammonium chloride is 1:5, fully stirring and mixing for 1 hour, performing centrifugal separation, washing with deionized water to remove physically adsorbed polydiallyldimethyl ammonium chloride, then placing in an argon atmosphere, and drying at 40 ℃ to obtain a carbon nano tube with positive charges;
(2) sequentially adding ferrous chloride, oxalic acid and ascorbic acid into a mixed solution (volume ratio is 1: 1) of ethanol and deionized water, and stirring for 48 hours at normal temperature to obtain a ferrous oxalate complex solution, wherein the molar ratio of the ferrous chloride to the oxalic acid is 1:5, and the molar ratio of the ferrous chloride to the ascorbic acid is 10: 1;
(3) adding the carbon nano tube with positive charges in the step (1) into the ferrous oxalate complex solution in the step (2), wherein the mass ratio of the carbon nano tube with positive charges to the ferrous oxalate complex is 1:30, stirring for 30min at normal temperature, slowly adding copper chloride into the mixed solution, wherein the molar ratio of the copper chloride to the ferrous chloride is 1:2, continuously stirring and mixing for 1h, transferring into a high-temperature high-pressure reaction kettle, reacting for 24h at 60 ℃, filtering, washing and drying after the reaction is finished and naturally cooled to obtain Fe 2/3 Cu 1/3 C2O4/MWCNTs·yH2O precursor;
(4) under the argon atmosphere, Fe obtained in the step (3) 2/3 Cu 1/3 C2O4/MWCNTs·yH2And (3) placing the O precursor in a vacuum tube furnace, and sintering for 3h at 300 ℃ to obtain the carbon nano tube and metal copper co-doped ferrous weed lithium ion battery composite negative electrode material.
The scanning electron microscope and the projection electron microscope of the cathode material of the lithium ion battery with the co-doped ferrous oxalate of the carbon nano tube and the metallic copper are shown in fig. 3, and it can be obviously observed that the nano spherical metallic copper particles are uniformly filled around the rod-shaped ferrous oxalate particles, and the carbon nano tube shuttles to the edge of the rotating particles; the TG thermogravimetric curve of the negative electrode material of this example is shown in fig. 1a, from which it can be seen that the carbon nanotube and metallic copper co-doped ferrous oxalate composite material shows significantly different crystallization water temperatures and oxalate decomposition temperatures.
Weighing 0.3g of the composite material prepared in the embodiment, 0.15g of acetylene black and 0.05g of polyvinylidene fluoride (PVDF), putting the materials into a mortar, grinding for 30min, adding 1ml of N-methyl-2-pyrrolidone solution, continuously grinding for 20min, uniformly coating a viscous mixture on a copper foil, primarily drying the mixture at 80 ℃ for 15min, drying the mixture in a vacuum oven at 80 ℃ for 12h, rolling the copper foil, and cutting the mixture into a wafer with the diameter of 14mm to obtain a pole piece.
In a glove box filled with argon (O)2Content < 1ppm, water content < 1 ppm), assembling the pole piece, the diaphragm, the lithium piece and the foam nickel net into a button cell by a conventional method, carrying out a battery electrochemical performance test on a constant current charging and discharging system at a rate of 1C =1000mA/g, and showing a multiplying power cycle result chart in fig. 4 (a), wherein the multiplying power cycle result chart is shown in 0.2, 0.5, 1, 2, 3 and 5A g-1Under the current density, the carbon nano tube and metal copper co-doped ferrous oxalate composite material shows excellent rate performance, and the specific discharge capacities of the carbon nano tube and metal copper co-doped ferrous oxalate composite material are 970 mAh g, 830 mAh, 760 mAh, 690 mAh, 640 mAh and 560mAh g respectively-1Specific discharge capacity of (2).
Example 2: the preparation method of the carbon nanotube and metal copper co-doped ferrous weed acid lithium ion battery composite negative electrode material comprises the following steps:
(1) sequentially adding a surfactant cetyl trimethyl ammonium bromide and a carbon nano tube into a mixed solution (volume ratio is 1: 1) of ethanol and deionized water, wherein the mass ratio of the surfactant to the carbon nano tube is 1:5, performing ultrasonic treatment at normal temperature for 4 hours, dropwise adding a polydiallyldimethylammonium chloride aqueous solution with the concentration of 1mg/mL, wherein the mass ratio of the carbon nano tube to the polydiallyldimethylammonium chloride is 1:10, fully stirring and mixing for 2 hours, performing centrifugal separation, washing with deionized water to remove physically adsorbed polydiallyldimethylammonium chloride, then placing in an inert gas atmosphere, and drying at 50 ℃ to obtain a positively charged carbon nano tube;
(2) sequentially adding ferrous sulfate, oxalic acid and ascorbic acid into a mixed solution (volume ratio is 1: 1) of ethanol and deionized water, and stirring for 30 hours at normal temperature to obtain a ferrous oxalate complex solution, wherein the molar ratio of the ferrous sulfate to the oxalic acid is 1:8, and the molar ratio of the ferrous chloride to the ascorbic acid is 5: 1;
(3) adding the carbon nano tube with positive charges in the step (1) into the ferrous oxalate complex solution in the step (2), wherein the mass ratio of the carbon nano tube with positive charges to the ferrous oxalate complex is 1:20, stirring for 30min at normal temperature, slowly adding copper sulfate into the mixed solution, wherein the molar ratio of the copper sulfate to the ferrous sulfate is 1:5, continuously stirring and mixing for 1.5h, transferring into a high-temperature high-pressure reaction kettle, reacting for 8h at 100 ℃, filtering, washing and drying after the reaction is finished and the natural cooling are carried out, so as to obtain Fe 5/6 Cu 1/6 C2O4/MWCNTs·2H2O precursor;
(4) under the argon atmosphere, Fe obtained in the step (3) 5/6 Cu 1/6 C2O4/MWCNTs·2H2And (3) placing the O precursor in a vacuum tube furnace, and sintering for 5h at 200 ℃ to obtain the carbon nano tube and metal copper co-doped ferrous weed lithium ion battery composite negative electrode material.
The X-ray diffraction pattern of the cathode material of the lithium ion battery with the carbon nano tube and the metal copper co-doped ferrous oxalate prepared by the embodiment is shown in figure 2, and the low diffraction peak intensity of the carbon nano tube can be still seen, which indicates that the ferrous oxalate and the carbon nano tube are effectively compounded; the TG thermogravimetric curve of the negative electrode material of this embodiment is shown in fig. 1b, and it can be seen from the graph that the ferrous oxalate structure of the carbon nanotube and metal copper co-doped ferrous oxalate negative electrode material is not damaged in the heat treatment process.
Weighing 0.3g of the composite material prepared in the embodiment, 0.15g of acetylene black and 0.05g of polyvinylidene fluoride (PVDF), putting the materials into a mortar, grinding for 30min, adding 1ml of N-methyl-2-pyrrolidone solution, continuously grinding for 20min, uniformly coating a viscous mixture on a copper foil, primarily drying the mixture at 80 ℃ for 15min, drying the mixture in a vacuum oven at 80 ℃ for 12h, rolling the copper foil, and cutting the mixture into a wafer with the diameter of 14mm to obtain a pole piece.
In a glove box filled with argon (O)2Content < 1ppm, water content < 1 ppm), assembling the pole piece, the diaphragm, the lithium piece and the foam nickel net into a button cell by a conventional method, carrying out a battery electrochemical performance test on a constant current charging and discharging system at a rate of 1C =1000mA/g, and showing a multiplying power cycle result chart in figure 4 (b), wherein the multiplying power cycle result chart is shown in figure 1A g-1Under the current density, the carbon nano tube and metal copper co-doped ferrous oxalate composite material shows excellent small current circulation performance, and the discharge specific capacity at the later stage of 100 cycles is 680mAh g-1。
Example 3: the preparation method of the carbon nanotube and metal copper co-doped ferrous weed acid lithium ion battery composite negative electrode material comprises the following steps:
(1) sequentially adding a surfactant cetyl trimethyl ammonium bromide and a carbon nano tube into a mixed solution (volume ratio is 1: 1) of ethanol and deionized water, wherein the mass ratio of the surfactant to the carbon nano tube is 1:20, carrying out ultrasonic treatment at normal temperature for 5 hours, dropwise adding a polydiallyldimethylammonium chloride aqueous solution with the concentration of 5mg/mL, wherein the mass ratio of the carbon nano tube to the polydiallyldimethylammonium chloride is 1:15, fully stirring and mixing for 3 hours, carrying out centrifugal separation, washing with deionized water to remove physically adsorbed polydiallyldimethylammonium chloride, then placing in an inert gas atmosphere, and drying at 60 ℃ to obtain a positively charged carbon nano tube;
(2) sequentially adding ferrous nitrate, oxalic acid and ascorbic acid into a mixed solution of ethanol and deionized water, and stirring at normal temperature for 40 hours to obtain a ferrous oxalate complex solution, wherein the molar ratio of the ferrous nitrate to the oxalic acid is 1:10, and the molar ratio of the ferrous chloride to the ascorbic acid is 10: 1;
(3) adding the carbon nano tubes with positive charges in the step (1) into the ferrous oxalate complex solution in the step (2), wherein the mass ratio of the carbon nano tubes with positive charges to the ferrous oxalate complex is 1:10, stirring for 30min at normal temperature, and slowly adding copper nitrate into the mixed solution, wherein the molar ratio of the copper nitrate to the ferrous nitrate isThe ratio is 1:9, the mixture is continuously stirred and mixed for 2h, then the mixture is moved into a high-temperature high-pressure reaction kettle to react for 6h at the temperature of 150 ℃, and after the reaction is finished and the mixture is naturally cooled, the mixture is filtered, washed and dried to obtain Fe 9/10 Cu 1/10 C2O4/MWCNTs·yH2O precursor;
(4) under nitrogen atmosphere, Fe obtained in the step (3) 9/10 Cu 1/10 C2O4/MWCNTs·yH2And (3) placing the O precursor in a vacuum tube furnace, and sintering for 4h at 250 ℃ to obtain the carbon nano tube and metal copper co-doped ferrous weed lithium ion battery composite negative electrode material.
Weighing 0.3g of the composite material prepared in the embodiment, 0.15g of acetylene black and 0.05g of polyvinylidene fluoride (PVDF), putting the materials into a mortar, grinding for 30min, adding 1ml of N-methyl-2-pyrrolidone solution, continuously grinding for 20min, uniformly coating a viscous mixture on a copper foil, primarily drying the mixture at 80 ℃ for 15min, drying the mixture in a vacuum oven at 80 ℃ for 12h, rolling the copper foil, and cutting the mixture into a wafer with the diameter of 14mm to obtain a pole piece.
In a glove box filled with argon (O)2Content < 1ppm, water content < 1 ppm), assembling the pole piece, the diaphragm, the lithium piece and the foam nickel net into a button cell by a conventional method, carrying out a battery electrochemical performance test on a constant current charging and discharging system at a rate of 1C =1000mA/g, and showing a multiplying power cycle result chart in fig. 4C, wherein the multiplying power cycle result chart is shown in 5A g-1Under the current density, the carbon nano tube and metal copper co-doped ferrous oxalate composite material shows excellent small current circulation performance, and the discharge specific capacity at the later stage of 100 cycles is 580mAh g-1And the cycle performance is excellent.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.

Claims (5)

1. A preparation method of a carbon nanotube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material is characterized by comprising the following specific steps:
(1) sequentially adding a surfactant cetyl trimethyl ammonium bromide and a carbon nano tube into a mixed solution of ethanol and deionized water, wherein the mass ratio of the surfactant to the carbon nano tube is 1: 5-1: 20, carrying out ultrasonic treatment at normal temperature for 3-5 h, dropwise adding a polydiallyldimethyl ammonium chloride aqueous solution with the concentration of 0.2-10 mg/mL, wherein the mass ratio of the carbon nano tube to the polydiallyldimethyl ammonium chloride is 1: 5-1: 20, fully stirring and mixing for 1-3 h, carrying out centrifugal separation, washing with deionized water to remove physically adsorbed polydiallyldimethyl ammonium chloride, then placing in an inert gas atmosphere, and drying at 40-60 ℃ to obtain a positively charged carbon nano tube;
(2) sequentially adding soluble ferrous salt, oxalic acid and ascorbic acid into a mixed solution of ethanol and deionized water, and stirring for 24-52 hours at normal temperature to obtain a ferrous oxalate complex solution, wherein the molar ratio of the soluble ferrous salt to the oxalic acid is 1: 5-1: 10;
(3) adding the carbon nano tube with positive charges in the step (1) into the ferrous oxalate complex solution in the step (2), stirring the mixture at normal temperature for 30min, slowly adding soluble copper salt into the mixed solution, wherein the mass ratio of the carbon nano tube with positive charges to the ferrous oxalate complex is 1: 30-1: 10, the molar ratio of the soluble copper salt to the soluble ferrous salt is 1: 1-1: 9, continuously stirring and mixing the mixture for 1-2 h, transferring the mixture into a high-temperature high-pressure reaction kettle, reacting the mixture for 6-24 h at the temperature of 60-150 ℃, filtering, washing and drying the mixture after the reaction is finished and the mixture is naturally cooled to obtain Fe x Cu 1-x C2O4/MWCNTs·yH2O precursor;
(4) under the atmosphere of argon or nitrogen, Fe obtained in the step (3) x Cu 1-x C2O4/MWCNTs·yH2And (3) placing the O precursor in a vacuum tube furnace, and sintering at 200-300 ℃ for 1-6 h to obtain the carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material.
2. The preparation method of the carbon nanotube and metal copper co-doped lithium iron oxalate battery composite anode material according to claim 1, characterized in that: the soluble ferrous salt is one or more of ferrous chloride, ferrous sulfate, ferrous nitrate and ferrous acetate in any ratio; the soluble copper salt is one or more of copper chloride, copper sulfate, copper nitrate and copper acetate.
3. The preparation method of the carbon nanotube and metal copper co-doped lithium iron oxalate battery composite anode material according to claim 1, characterized in that: the mixed liquid of the ethanol and the deionized water is prepared by mixing the ethanol and the deionized water according to the volume ratio of 1: 1.
4. The preparation method of the carbon nanotube and metal copper co-doped lithium iron oxalate battery composite anode material according to claim 1, characterized in that: the molar ratio of the soluble ferrous salt to the oxalic acid is 1: 5-1: 10, and the molar ratio of the soluble ferrous salt to the ascorbic acid is 5: 1-10: 1.
5. The carbon nanotube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material prepared by the preparation method of the carbon nanotube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material of any one of claims 1 to 4.
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