CN113036101A - Carbon-coated pyrophosphate and preparation method and application thereof - Google Patents
Carbon-coated pyrophosphate and preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a carbon-coated pyrophosphate and a preparation method and application thereof, wherein the chemical general formula of the carbon-coated pyrophosphate is M2P2O7@ C; wherein M is at least one selected from transition metal elements and IVA group metal elements. The carbon-coated pyrophosphate material provided by the application has the advantages of uniform particle size, good crystallinity, excellent electrochemical performance, simple preparation method process, mild condition, less pollution, low energy consumption and easiness in large-scale production. The carbon-coated pyrophosphate is used as the negative electrode material of the lithium/sodium ion battery, and the obtained battery has high charge-discharge specific capacityAnd the cycle performance is excellent.
Description
Technical Field
The application relates to a carbon-coated pyrophosphate and a preparation method and application thereof, belonging to the technical field of battery electrode materials.
Background
The high energy conversion efficiency and high mass/volume energy density of Lithium Ion Batteries (LIBs) bring great convenience to our modern life. However, the insufficient reserves of lithium resources are not widespread worldwide limiting their further applications. According to the statistics and prediction of Gunther Martin et al, the demand of lithium for the battery in 2015 is about 53629 tons (calculated based on the mass of lithium carbonate equivalent), and the demand increases by 7% in 2020 to 76637 tons, which accounts for 34% of the total lithium output, which reflects the reason why the price of lithium carbonate is increasing since 2010 from side. From the viewpoint of saving lithium resources and reducing the price of battery modules of electric vehicles, on one hand, the utilization rate of lithium resources needs to be improved, and on the other hand, a suitable secondary battery system needs to be found to replace a lithium ion battery.
The foundation for improving the utilization rate of the lithium resource lies in further improving the quality energy density of the lithium ion battery, for example, selecting a positive/negative electrode material with higher theoretical capacity, matching high-voltage electrolyte to improve the working voltage of the lithium ion single battery and the like; sodium ion batteries have the same working principle as lithium ion batteries, and the standard electrode potential of metal sodium is only slightly lower than that of metal lithium (-2.71V vs. -3.04V), and in addition, the abundance of sodium resources in the earth crust is hundreds of times that of lithium resources (2.36% vs. 0.002%), so the sodium ion secondary batteries are one of potential candidate systems of the lithium ion batteries.
The capacity of the graphite negative electrode of the current commercial lithium ion battery is close to the theoretical specific capacity, and the demand of people for the high-energy density lithium ion battery can not be met gradually, so that the development of a negative electrode material with higher specific capacity is urgently needed. Alloy type materials, silicon and tin, although having extremely high theoretical specific capacity, the inherent higher volume expansion and lower ionic conductivity of this type of material limit their application; the metal oxygen/sulfur/phosphide belongs to a conversion type material, although the theoretical capacity is also higher, the average working voltage is high, the average working voltage and the energy density of the lithium ion battery are reduced, the material preparation process is complicated, the energy consumption is high, and the pollution is large in the preparation process of sulfide and phosphide.
Disclosure of Invention
According to one aspect of the application, the carbon-coated pyrophosphate has uniform particle size, good crystallinity and excellent electrochemical performance, and when the carbon-coated pyrophosphate is applied to a lithium/sodium ion battery, the battery has high charge-discharge specific capacity and excellent cycle performance.
The chemical general formula of the carbon-coated pyrophosphate is M2P2O7@C；
Wherein M is at least one selected from transition metal elements and IVA group metal elements.
Alternatively, the transition metal element is a metal element having a +2 valence state;
the metallic element of IVA group is at least one of Ge, Sn and Pb;
the transition metal element is at least one selected from Ni, Co, Fe, Cu, Mn, Zn, Cr and Mo.
Alternatively, the microstructure of the carbon-coated pyrophosphate is a spheroidal nanoparticle.
Optionally, the particle size of the nanoparticles is 100-300 nm.
According to yet another aspect of the present application, there is provided a method for preparing the carbon-coated pyrophosphate, the method comprising at least the steps of:
step 1, reacting a mixture containing a phosphorus source, an M source and a carbon source to obtain a precursor product;
and 2, calcining the precursor product in a protective atmosphere to obtain the carbon-coated pyrophosphate.
Optionally, the molar ratio of the phosphorus source to the M source is 0.8-1.5: 1; preferably, the molar ratio of the phosphorus source to the M source is 1-1.2: 1;
the molar ratio of the M source to the carbon source is 1: 0.2-3.0; preferably, the molar ratio of the M source to the carbon source is 1: 0.2-0.6;
wherein, the dosage of the phosphorus source is calculated by the mole number of the phosphorus element, the dosage of the M source is calculated by the mole number of the metal element, and the dosage of the carbon source is calculated by the mole number of the carbon source substance.
Specifically, the molar ratio of the phosphorus source to the M source may be independently selected from 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, or any value therebetween.
Specifically, the lower limit of the molar ratio of the M source to the carbon source can be independently selected from 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1: 0.6; the upper limit of the molar ratio of the M source to the carbon source may be independently selected from 1:1.0, 1:1.5, 1:2.0, 1:2.5, 1: 3.0.
Alternatively, the phosphorus source is organic phosphorus;
preferably, the organic phosphorus is selected from any one of aminotrimethylene phosphoric acid, phytic acid, tributyl phosphate, triethyl phosphate, triphenyl phosphate and tricresyl phosphate;
the M source is selected from salts corresponding to metal elements;
preferably, the salt corresponding to the metal element is selected from any one of nitrate, acetate, chloride, sulfate and oxalate;
the carbon source is selected from any one of carbohydrate, coal tar pitch, oleic acid and organic compounds containing heterocyclic rings or benzene rings;
preferably, the saccharide is selected from at least one of glucose and sucrose;
preferably, the organic compound containing heterocyclic ring or benzene ring is selected from any one of dopamine hydrochloride, pyrrole, styrene and aniline.
Optionally, step 1 comprises:
1.1 mixing a solution I containing a phosphorus source and a solution II containing an M source to perform a reaction A to obtain a mixed reactant;
1.2 adding a solution III containing a carbon source into the mixed reactant to perform a reaction B, thereby obtaining the precursor product.
Alternatively, the conditions of reaction a are: the reaction temperature is 10-50 ℃, and the reaction time is 6-12 h;
preferably, the solution I containing the phosphorus source is dripped into the solution II containing the M source at the dripping speed of 1-10 mL/min; the dripping speed influences the size of the finally formed nano particles, and further preferably, the dripping speed is 2-4 mL/min;
the conditions of reaction B were: the reaction temperature is 10-50 ℃, and the reaction time is 8-24 h.
Specifically, stirring and reacting for 6-12 h after the dropwise adding is completed.
Specifically, in the reaction A, the lower limit of the reaction time can be independently selected from 10 ℃, 15 ℃, 20 ℃, 25 ℃ and 30 ℃; the upper limit of the reaction time may be independently selected from 35 deg.C, 40 deg.C, 42 deg.C, 45 deg.C, and 50 deg.C.
Specifically, in the reaction a, the reaction time may be independently selected from 6h, 7h, 8h, 9h, 10h, 11h, 12h, or any value between the above two points.
Specifically, in the reaction A, the lower limit of the dropping speed of the solution I containing the phosphorus source can be independently selected from 1mL/min, 2mL/min, 3mL/min, 4mL/min and 5 mL/min; the upper limit of the dropping speed of the solution I containing the phosphorus source can be independently selected from 6mL/min, 7mL/min, 8mL/min, 9mL/min and 10 mL/min.
Specifically, in the reaction A, the lower limit of the reaction time can be independently selected from 10 ℃, 15 ℃, 20 ℃, 25 ℃ and 30 ℃; the upper limit of the reaction time may be independently selected from 35 deg.C, 40 deg.C, 42 deg.C, 45 deg.C, and 50 deg.C.
Specifically, in the reaction B, the lower limit of the reaction time can be independently selected from 8h, 10h, 12h, 14h and 15 h; the upper limit of the reaction time can be independently selected from 16h, 18h, 20h, 22h, 24 h.
Optionally, stirring is carried out during the reaction A, and the stirring speed is 300-700 rmp.
Specifically, the stirring speed may be independently selected from 300rmp, 400rmp, 500rmp, 600rmp, 700rmp, or any point value between the above two points.
Optionally, in the solution I, the concentration of the phosphorus source is 0.025-0.3 mol/L;
in the solution II, the concentration of the M source is 0.0375-0.15 mol/L;
in the solution III, the concentration of the carbon source is 0.01-1.0 mol/L.
Specifically, the lower limit of the concentration of the phosphorus source can be independently selected from 0.025mol/L, 0.05mol/L, 0.067mol/L, 0.08mol/L, 0.1 mol/L; the upper concentration limit of the phosphorus source can be independently selected from 0.12mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L and 0.3 mol/L.
Specifically, the lower concentration limit of the M source can be independently selected from 0.0375mol/L, 0.045mol/L, 0.05mol/L, 0.075mol/L and 0.1 mol/L; the upper concentration limit of the M source can be independently selected from 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L and 0.15 mol/L.
Specifically, the lower limit of the concentration of the carbon source may be independently selected from 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.24mol/L, 0.33 mol/L; the upper limit of the concentration of the carbon source may be independently selected from 0.48mol/L, 0.5mol/L, 0.7mol/L, 0.9mol/L, and 1.0 mol/L.
Optionally, in the solution I and the solution II, the solvent is independently selected from at least one of amide compounds, sulfone compounds and ether compounds;
preferably, the solvent of solution I and solution II is the same;
in the solution III, the solvent is at least one selected from water, alcohol compounds, amide compounds, sulfone compounds and ether compounds.
Optionally, the amide compound is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
the sulfur-containing organic compound comprises dimethyl sulfoxide;
the ether compound comprises tetrahydrofuran;
the alcohol compound is at least one of ethanol, isopropanol, n-propanol and isobutanol.
Alternatively, in step 2, the calcination conditions are:
the calcination temperature is 500-800 ℃, and the heat preservation time is 1-10 h;
preferably, the calcination temperature is 550-750 ℃, and the heat preservation time is 2-4 h.
Specifically, the lower limit of the calcination temperature may be independently selected from 500 ℃, 550 ℃, 580 ℃, 600 ℃, 620 ℃; the upper limit of the calcination temperature may be independently selected from 650 ℃, 680 ℃, 700 ℃, 750 ℃, 800 ℃.
Specifically, the holding time may be independently selected from 2h, 2.5h, 3h, 3.5h, 4h, or any value between the above two points.
Optionally, the heating rate of the calcination is 1-10 ℃/min;
preferably, the heating rate is 2-5 ℃/min.
Specifically, the lower limit of the heating rate can be independently selected from 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min and 5 ℃/min; the upper limit of the heating rate can be independently selected from 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min and 10 ℃/min.
Optionally, the protective atmosphere is an inert gas selected from argon or nitrogen.
Optionally, the method further comprises:
drying the precursor product prior to the calcining;
preferably, the drying temperature is 50-90 ℃, and the drying time is 6-12 h.
Specifically, after the reaction B is finished, a precursor product is separated by suction filtration or evaporation to dryness and dried.
Specifically, the lower limit of the drying temperature can be independently selected from 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C; the upper limit of the drying temperature can be independently selected from 75 deg.C, 78 deg.C, 80 deg.C, 85 deg.C, and 90 deg.C.
Specifically, the drying time may be independently selected from 6h, 7h, 8h, 9h, 10h, 11h, 12h, or any value therebetween.
In the present application, "M2P2O7In the structural formula of @ C `, ` M2P2O7"indicates the internal pyrophosphate material," C "indicates a carbon layer obtained by heat-treating a polymer in a precursor," @ "indicates the coating relationship of the external carbon layer with respect to the internal pyrophosphate.
According to still another aspect of the present application, there is provided a negative electrode material comprising any of the carbon-coated pyrophosphate described above, the carbon-coated pyrophosphate prepared by any of the methods described above.
According to still another aspect of the present application, there is provided a battery including the above-described anode material;
the battery is a lithium ion battery or a sodium ion battery.
The beneficial effects that this application can produce include:
1) the carbon-coated pyrophosphate material provided by the application has the advantages of uniform particle size, good crystallinity and excellent electrochemical performance.
2) The preparation method of the carbon-coated pyrophosphate material provided by the application has the advantages of simple process, mild condition, less pollution, low energy consumption and easiness in large-scale production.
3) When the carbon-coated pyrophosphate provided by the application is used as a negative electrode material of a lithium/sodium ion battery, the carbon-coated pyrophosphate belongs to a conversion type material, not only has higher specific capacity, but also can maintain the structural stability of a stable pyrophosphate framework; meanwhile, the capacitance characteristic of the pyrophosphate endows the material with excellent rate performance.
Drawings
FIG. 1 is an XRD pattern of carbon-coated cobalt pyrophosphate obtained in example 1;
FIG. 2 is an SEM photograph of carbon-coated cobalt pyrophosphate obtained in example 1;
FIG. 3 is a TEM image of carbon-coated cobalt pyrophosphate obtained in example 1;
FIG. 4 is a graph of the cycling performance of the carbon-coated cobalt pyrophosphate material obtained in example 1 as a negative electrode of a sodium ion battery at a current density of 1000 mA/g;
FIG. 5 is an XRD pattern of carbon-coated manganese pyrophosphate obtained in example 2;
FIG. 6 is a graph of the cycling performance of the carbon-coated manganese pyrophosphate material obtained in example 2 as a negative electrode of a lithium ion battery at a current density of 100 mA/g;
FIG. 7 is an SEM photograph of cobalt pyrophosphate obtained in comparative example 1 without carbon coating;
FIG. 8 is a graph showing the cycle characteristics of the cobalt pyrophosphate material without carbon coating obtained in comparative example 1 as a negative electrode of a sodium ion battery at a current density of 1000 mA/g.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the starting materials in the examples of the present application were purchased commercially, and reagents such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, tetrahydrofuran, nitrate, acetate, oxalate and the like in the preparation of the materials were purchased from Arlatin or the group of national drugsChemical agents, Inc., Celgard2320 lithium battery separator was purchased from Celgard, USA, and the glass fiber was Whatman brand. Coal tar pitch (not less than 99%) is purchased from Jinluno chemical Co., Ltd. in Jinan, and has an average molecular formula of C15H28O2。
The analysis method and apparatus in the embodiments of the present application are as follows: SEM analysis is carried out by using a Japanese Hitachi S4800 cold field emission scanning electron microscope, TEM analysis is carried out by using a Tecnai F20 transmission electron microscope of FEI company in America, XRD analysis is carried out by using a D8 advanced Davince X-ray powder diffractometer of Bruker company in Germany, and electrochemical performance analysis is carried out by using a CT2100A battery test system of Wuhan blue electric company.
Example 1:
dissolving 1mmol of aminotrimethylene phosphate in 20mL of DMF solution to obtain colorless transparent clear solution I; dissolving 3mmol of cobalt acetate tetrahydrate in 20mL of DMF solution to obtain a purple clear transparent solution II; 1mmol dopamine hydrochloride was dissolved in 3mL DMF to obtain solution III. Slowly dripping the solution I into the solution II at the temperature of 25 ℃ at the speed of 2mL/min, simultaneously keeping the stirring speed of the solution II at 450rmp, continuously stirring for 8 hours after finishing dripping, then keeping the reaction temperature unchanged, adding the solution III, continuously stirring for 12 hours, and performing suction filtration and separation to obtain a precursor product. Drying in a vacuum drying oven at 80 deg.C for 12 hr, grinding in a mortar, transferring into a tube furnace, heating to 700 deg.C at a heating rate of 3 deg.C/min, and maintaining for 2 hr to obtain final product, Co2P2O7@ C material, designated sample # 1.
XRD analysis of sample # 1 showed that the final product was pure phase Co as shown in FIG. 12P2O7Material, no other miscellaneous peaks. SEM analysis is carried out on the sample No. 1, and as shown in figure 2, the carbon-coated cobalt pyrophosphate is spherical-like particles with the size of 100-300 nm, the particle dispersibility is good, and no obvious agglomeration phenomenon exists. TEM analysis of sample # 1, shown in FIG. 3, surface carbon layer vs. Co2P2O7The particles are evenly and completely coated. These characterizations demonstrate that carbon-coated cobalt pyrophosphate particles of uniform size and good dispersibility can be prepared by the above method.
And (3) mixing the prepared carbon-coated cobalt pyrophosphate material with an active substance, namely carbon-coated cobalt pyrophosphate: conductive agent Super P: uniformly mixing sodium carboxymethylcellulose CMC (sodium carboxymethyl cellulose) in a mass ratio of 8:1:1, adding deionized water as a solvent to prepare slurry, uniformly coating the slurry on a copper foil, performing vacuum drying at 80 ℃ for 12h, and blanking into a wafer with the diameter of 12mm to assemble the sodium-ion battery. The battery case used for assembly is CR2016 type, metal sodium is used as a counter electrode, glass fiber is used as a diaphragm, and the electrolyte is 1M NaClO4Dissolved in 100 Vol% polycarbonate PC + 5% fluoroethylene carbonate FEC (i.e., PC + FEC + NaClO)4In solution of composition, NaClO4The concentration of (3) is 1M).
And after the assembled sodium ion battery is kept stand for 12 hours, performing charge and discharge tests under the current density of 1000mA/g, wherein the test voltage range is 0.01-3.0V. The initial discharge capacity is 500.8mAh/g, the initial discharge specific capacity of 1A/g is 313mAh/g, the discharge specific capacity of 500 times of circulation is 205mAh/g, and the cycle performance result is shown in figure 4.
Example 2:
dissolving 1mmol of aminotrimethylene phosphate in 20mL of DMF solution to obtain colorless transparent clear solution I; dissolving 3mmol of manganese nitrate tetrahydrate in 40mL of DMF solution to obtain a light red clear transparent solution II; 1.2mmol dopamine hydrochloride was dissolved in 5mL DMF solution to obtain solution III. Slowly dripping the solution I into the solution II at the temperature of 25 ℃ at the speed of 3mL/min, simultaneously keeping the stirring speed of the solution II at 500rmp, continuously stirring for 8 hours after finishing dripping, then keeping the reaction temperature unchanged, adding the solution III, continuously stirring for 12 hours, and performing suction filtration and separation to obtain a precursor product. Drying in a vacuum drying oven at 60 deg.C for 12h, grinding in a mortar, transferring into a tube furnace, heating to 600 deg.C at a heating rate of 2 deg.C/min, and maintaining for 2h to obtain final product, i.e. Mn2P2O7@ C material, designated sample # 2.
XRD analysis of sample No. 2 resulted in pure phase Mn as shown in FIG. 52P2O7Material, no other miscellaneous peaks. The SEM and TEM analysis results of sample No. 2 are similar to those of sample No. 1.
To be preparedA carbon-coated manganese pyrophosphate material, wherein the ratio of active carbon-coated manganese pyrophosphate: conductive agent Super P: uniformly mixing sodium carboxymethylcellulose CMC (8: 1: 1) in mass ratio, adding deionized water as a solvent to prepare slurry, uniformly coating the slurry on a copper foil, performing vacuum drying at 90 ℃ for 12 hours, and blanking into round pieces with the diameter of 12mm to assemble the lithium ion battery. The battery case used for assembly is CR2032 type, metal lithium is used as a counter electrode, Celgard2320 diaphragm, and electrolyte is 1M LiPF6Dissolved in EC/EMC/DMC (i.e., EC + EMC + DMC + LiPF)6In solution of composition, LiPF6The concentration of (3) is 1M).
And after the assembled lithium ion battery is kept stand for 12 hours, performing charge and discharge tests under the current density of 100mA/g, wherein the test voltage range is 0.01-3.0V. The initial discharge capacity was 823mAh/g, the specific discharge capacity after 100 cycles was 421mAh/g, and the cycle performance results are shown in FIG. 6.
Example 3:
dissolving 1.2mmol of phytic acid in 30mL of NMP solution to obtain a colorless transparent clear solution I; dissolving 3mmol of manganese acetate tetrahydrate and 3mmol of cobalt acetate tetrahydrate in 60mL of NMP solution to obtain a clear solution II; 2.4mmol dopamine hydrochloride was dissolved in 5mL NMP solution to obtain solution III. Slowly dripping the solution I into the solution II at the temperature of 40 ℃ at the speed of 2.5mL/min, keeping the stirring speed of the solution II at 600rmp, continuing stirring for 12 hours after finishing dripping, keeping the reaction temperature unchanged, adding the solution III, continuing stirring for 16 hours, and performing suction filtration and separation to obtain a precursor product. Drying in a vacuum drying oven at 80 deg.C for 12h, grinding in a mortar, transferring into a tube furnace, heating to 650 deg.C at a heating rate of 4 deg.C/min, and maintaining for 3h to obtain final product, i.e. CoMnP2O7@ C material.
Example 4:
dissolving 1mmol of aminotrimethylene phosphate in 20mL of DMF solution to obtain colorless transparent clear solution I; dissolving 3mmol of cobalt acetate tetrahydrate in 20mL of DMF solution to obtain a purple clear transparent solution II; 200mg of coal tar pitch was dissolved in 40mL of tetrahydrofuran to obtain solution III. Slowly dripping the solution I into the solution II at the temperature of 15 ℃ at the speed of 2mL/min, keeping the stirring speed of the solution II at 450rmp, continuing stirring for 12h after finishing dripping, performing suction filtration to separate a solid product, keeping the reaction temperature unchanged, adding into the solution III, performing sealed ultrasonic treatment for 1h, continuing stirring for 12h, transferring a reaction vessel into a fume hood, and evaporating the solution in an oil bath at the temperature of 40 ℃ to dryness to obtain a precursor product. Drying in a vacuum drying oven at 80 ℃ for 12h, grinding in a mortar, transferring into a tube furnace, heating to 700 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 2h to obtain a final product, namely the carbon-coated cobalt pyrophosphate material.
Comparative example 1:
in comparison with example 1, the same procedure was followed except that no carbon source-containing solution III was added, and cobalt pyrophosphate particles without carbon coating were obtained after calcination and were designated as sample No. D1.
By SEM analysis of sample D1#, as shown in FIG. 7, a significant increase in the particle size of the product was observed, and significant agglomeration was observed. The sodium ion battery assembled by the sample D1# is subjected to performance test, as shown in FIG. 8, the initial specific discharge capacity of the sodium ion battery is 393mAh/g, and 51.9mAh/g after 500 cycles, which is much lower than the specific discharge capacity of the carbon-coated cobalt pyrophosphate.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A carbon-coated pyrophosphate characterized in that said carbon-coated pyrophosphate has the chemical formula M2P2O7@C；
Wherein M is at least one selected from transition metal elements and IVA group metal elements.
2. The carbon-coated pyrophosphate according to claim 1, wherein said transition metal element is a metal element having a +2 valence state;
the IVA group metal element is at least one selected from Ge, Sn and Pb;
preferably, the transition metal element is at least one selected from the group consisting of Ni, Co, Fe, Cu, Mn, Zn, Cr, and Mo.
3. The carbon-coated pyrophosphate according to claim 1 wherein the microstructure of said carbon-coated pyrophosphate is spheroidal nanoparticles;
preferably, the particle size of the nano-particles is 100-300 nm.
4. The method of any one of claims 1 to 3, wherein the method comprises at least the steps of:
step 1, reacting a mixture containing a phosphorus source, an M source and a carbon source to obtain a precursor product;
and 2, calcining the precursor product in a protective atmosphere to obtain the carbon-coated pyrophosphate.
5. The preparation method according to claim 4, wherein the molar ratio of the phosphorus source to the M source is 0.8-1.5: 1;
the molar ratio of the M source to the carbon source is 1: 0.2-3.0;
wherein the dosage of the phosphorus source is calculated by the mole number of phosphorus element, the dosage of the M source is calculated by the mole number of metal element, and the dosage of the carbon source is calculated by the mole number of carbon source substance;
preferably, the phosphorus source is organic phosphorus;
the M source is selected from salts corresponding to metal elements;
the carbon source is selected from any one of carbohydrate, coal tar pitch, oleic acid and organic compounds containing heterocyclic rings or benzene rings;
further preferably, the organic phosphorus is selected from any one of aminotrimethylene phosphoric acid, phytic acid, tributyl phosphate, triethyl phosphate, triphenyl phosphate and tricresyl phosphate;
the salt corresponding to the metal element is selected from any one of nitrate, acetate, chloride, sulfate and oxalate;
the saccharide is selected from any one of glucose and sucrose;
the organic compound containing heterocyclic ring or benzene ring is selected from any one of dopamine hydrochloride, pyrrole, styrene and aniline.
6. The method according to claim 4, wherein the step 1 comprises:
1.1 mixing a solution I containing a phosphorus source and a solution II containing an M source to perform a reaction A to obtain a mixed reactant;
1.2 adding a solution III containing a carbon source into the mixed reactant to perform a reaction B, thereby obtaining the precursor product.
7. The production method according to claim 6,
the conditions of the reaction A are as follows: the reaction temperature is 10-50 ℃, and the reaction time is 6-12 h;
preferably, the solution I containing the phosphorus source is dripped into the solution II containing the M source at the dripping speed of 1-10 mL/min;
the conditions of the reaction B are as follows: the reaction temperature is 10-50 ℃, and the reaction time is 8-24 h;
preferably, in the solution I, the concentration of the phosphorus source is 0.025-0.3 mol/L;
in the solution II, the concentration of an M source is 0.0375-0.15 mol/L;
in the solution III, the concentration of a carbon source is 0.01-1.0 mol/L;
preferably, in the solution I and the solution II, the solvent is independently selected from at least one of amide compounds, sulfone compounds and ether compounds;
in the solution III, the solvent is at least one selected from water, alcohol compounds, amide compounds, sulfone compounds and ether compounds;
further preferably, the solvent of solution I and solution II is the same;
further preferably, the amide compound is at least one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
the sulfone compound comprises dimethyl sulfoxide;
the ether compound comprises tetrahydrofuran;
the alcohol compound is selected from any one of ethanol, isopropanol, n-propanol and isobutanol.
8. The method according to claim 4, wherein in step 2, the calcination is performed under the following conditions:
the calcination temperature is 500-800 ℃, and the heat preservation time is 1-10 h;
preferably, the calcining temperature is 550-750 ℃, and the heat preservation time is 2-4 h;
preferably, the temperature rise rate of the calcination is 1-10 ℃/min;
further preferably, the heating rate is 2-5 ℃/min;
preferably, the method further comprises:
drying the precursor product prior to the calcining;
preferably, the drying temperature is 50-90 ℃, and the drying time is 6-12 h.
9. A negative electrode material comprising the carbon-coated pyrophosphate according to any one of claims 1 to 3 and the carbon-coated pyrophosphate prepared by the method according to any one of claims 5 to 8.
10. A battery comprising the negative electrode material according to claim 9;
the battery is a lithium ion battery or a sodium ion battery.
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