WO2013178056A1

WO2013178056A1 - Positive electrode material and synthesis method thereof

Info

Publication number: WO2013178056A1
Application number: PCT/CN2013/076350
Authority: WO
Inventors: 岳敏; 刘祥; 王思敏; 黄友元
Original assignee: 深圳市贝特瑞新能源材料股份有限公司
Priority date: 2012-05-28
Filing date: 2013-05-28
Publication date: 2013-12-05
Also published as: CN102709553A; CN102709553B

Abstract

A positive electrode material CN/Li_xM_yM'_z(RO₄)_n, wherein the mass of a carbonitride compound, as the coating or doping material of the Li_xM_yM'_Z(RO₄)_ntype compound, is 0.1-30% of the CN/Li_xM_yM'_z(RO₄)_n; M is more than one of the elements Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn; M' is more than one of Mg, Ca, Al and Zn; and R is S, P or Si. The synthesis method of the positive electrode material comprises: mixing, and pyrolysis reaction under high temperature. Compared to prior art, using the carbonitride compound as coating or doping material can improve the conductivity of the electrode material, thus the conductivity is superior to that of the electrode material coated or doped with carbon material.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode material and a method of preparing the same, and more particularly to a cathode material and a preparation method thereof

law. Background technique

Li _x M _y M' _z (R0 ₄ ) _n type compound can be used as an electrode material of a lithium ion secondary battery and an electrochemical capacitor, wherein 0<x 3, 0^y^2, 0 z<0.5, ln 3, M is one or more elements in elements Nos. 21-30 of the periodic table, M, which is one or more elements of Mg, Ca, Al, and Z, and R is S, P, or Si.

Li _x M _y M' _z (R0 ₄ ) type compounds are characterized by generally low conductivity, preparation of electrode materials or electrodes, and the need to add conductive agents during use to increase their electrical conductivity, the type of conductive agent used in the prior art. There are carbon and metal, and metal conductive agents include Au and Ag. Metal-based conductive agents are expensive, so commonly used conductive agents are carbon-based conductive agents. In the prior art, in the preparation of the electrode material, an organic carbon source is added by coating or doping, and a conductive agent is formed by high-temperature carbonization treatment, or inorganic carbon is directly added to the electrode material when preparing the electrode. The above method does not improve the conductivity of the Li _x M _y M' _z (R0 ₄ ) _n type compound. SUMMARY OF THE INVENTION An object of the present invention is to provide a positive electrode material and a synthesis method thereof, which are to improve the electrical conductivity of a compound of Li _x M _y M' _z (R0 ₄ ) ₁₁ type. The invention adopts the following technical scheme: a positive electrode material having the general formula CN/Li _x M _y M' _z (R0 ₄ ) _n , coated or doped in a compound of Li _x M _y M' _z (R0 ₄ ) type Mixed with carbon and nitrogen compounds (CN), carbonitride The ratio of carbon to the element is 1-99.9%, the proportion of nitrogen to the element is 0.01-70%, and the mass of the carbon-nitrogen compound is 0.1% of the mass of CN/Li _x M _y M' _z (R0 ₄ ) _n -30%, wherein 0<x 3, 0^y^2, 0 z<0.5, ln 3, M is one of the elements Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn M or more, M is one or more of Mg, Ca, Al, and Zn, R is S, P or Si, and CN/Li _x M _y M' _z (R0 ₄ ) _n is an olivine structure or a Nasicon structure;

The carbonitride (CN) source is a carbon-nitrogen triple bond-containing compound acrylonitrile, polyacrylonitrile, acetonitrile, phenylacetonitrile, adiponitrile, cyanide, hydrocyanic acid, sodium cyanide, potassium cyanide, carbon-nitrogen-containing Double bond compound Schiff base, primary aldimine, secondary aldimine, primary ketimine, secondary ketimine, aldoxime, ketoxime, benzophenone oxime, carbonyl cyanide m-chlorobenzene腙, a compound containing carbon and nitrogen, pyridine, pyridine, pyrrole, pyrrole, nitrobenzene, phenol (picric acid), trinitrotoluene, trinitroresorcin, nitroglycerin, nitrosobenzene, a nitrosamine, an aldoxime, a ketoxime, a simple substance of carbon or a mixture of a carbon-containing compound and a nitrogen element or a nitrogen-containing compound, one or more of which;

The carbon-containing compound is an organic carbon source such as glucose, fructose, sucrose, maltose, sorbose, polyethylene glycol, polyvinyl alcohol, polyethylene, polypropylene, starch, cellulose and ester thereof, and ethylene-epoxyethylene oxime polymerization. Or a polymer of furanol, citric acid; inorganic carbon source acetylene black, carbon nanotubes, carbon nanofibers; gas carbon source is acetylene, formamidine, acetamidine;

The nitrogen-containing compound is nitric acid, nitrate, nitrous oxide, nitrogen monoxide, dinitrogen trioxide, nitrogen dioxide, dinitrogen tetroxide, and dinitrogen pentoxide. The nitrates are iron nitrate and lithium nitrate.

A method for synthesizing a positive electrode material includes the following steps:

1. Mixing, according to the Li element, the elements of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn contained in M, M, Mg, Ca, Al, Zn elements, R of S , P or Si element, the ratio of the amount of the substance: 0<Li 3 : 0 M 2 : 0 M, <0.5 : 1 R 3, CN source accounts for Li source, M source, M, source, R source and CN source 0.1-60% of the total mass of the precursor material, Li source, M source, M, The source, the R source and the CN source are mixed to obtain a precursor;

2. Put the precursor into a tube furnace, box furnace, rotary kiln, roller kiln or tunnel kiln, and carry out high temperature pyrolysis reaction under the protection of nitrogen, inert gas or reducing gas, at 0.8-18 °C. The heating rate of /min is raised from room temperature to 500-1100 ° C, the pyrolysis reaction is 1-72 h, and the furnace is naturally cooled to room temperature to obtain CN/ Li _x M _y M' _z (R0 ₄ ) no in Li _x M _y M ' _z (R0 ₄ )! ! The compound is coated or doped with a carbonitride CN, and the mass of CN is 0.1-30% of the mass of CN/Li _x M _y M' _z (R0 ₄ ) _n , wherein 0<x 3, 0 y 2, 0 z<0.5, ln 3, CN/ Li _x M _y M' _z (R0 ₄ ) _n is an olivine structure or a Nasicon structure;

The flow rate of the nitrogen, inert gas or reducing gas is 0.1-5000 L/min, the volume of oxygen in the furnace is below 200 ppm, the inert gas is argon or helium, and the reducing gas is hydrogen, carbon monoxide, acetylene, formazan or B. Hey.

The Li source of the present invention is at least one of lithium oxide, lithium hydroxide, lithium phosphate, lithium carbonate, lithium nitrate, lithium dihydrogen phosphate, lithium formate and lithium acetate;

The M source is one or more of a simple substance or a compound of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, wherein

The compound of the Sc is: cerium oxide, cerium oxalate, cerium sulfate;

The ruthenium compound is: titanium dioxide, titanium tetrachloride, titanium trichloride, metatitanic acid, titanium dicarbonyl titania, titanium fluoride, titanium oxynitride, titanyl sulfate;

The compound of V is: vanadium pentoxide, vanadium pentoxide, vanadium dioxide and vanadium pentoxide; the compound of Cr is: chromium oxide, chromium nitrate, chromium perchlorate, chromium sulfate;

The Mn compound is: manganese oxide, manganese dioxide, manganese dioxide, trimanganese tetraoxide, manganese dimanganese oxide, manganese chloride, permanganate, manganese carbonate, potassium manganate, ammonium manganese sulfate, sulfurization Manganese, manganese acetate, manganese trifluoride, manganese tetrafluoride, manganese nitrate, manganese sulfate; The Fe compound is: iron phosphate, ferrous sulfate, ferric oxide, ferrous oxide, triiron tetroxide, ammonium ferrous sulfate, ferrous sulfate, ferrous phosphate, ammonium ferrous phosphate, ferrous citrate , ferrocene, ferrous sulfide, ferrous phosphide, ferrous acetate, ferric sulphate, ferric nitrate, ferrous chloride, ferric chloride, ferrous hydroxide, ferrous carbonate, ferrous nitrate, ferrous oxalate, Ferrous perchlorate, iron hydroxide;

The compound of Co is: cobalt oxide, cobalt bromate, cobalt bromide, cobalt chlorate, cobalt chloride, cobalt fluoride, cobalt nitrate, cobalt nitrite, cobalt perchlorate, cobalt sulfate;

The Ni compound is: nickel oxide, nickel carbonate, nickel chlorate, nickel chloride, nickel fluoride, nickel nitrate, nickel perchlorate, nickel pyrophosphate, nickel sulfate;

The Cu compound is: copper oxide, cuprous chloride, cuprous cyanide, cuprous sulfide, cuprous thiocyanate, copper carbonate, copper chlorate, copper chloride, copper fluoride, copper formate, hydroxide Copper, copper nitrate, copper perchlorate, copper sulfate, copper sulfide;

The Zn compound is: zinc oxide, zinc acetate, zinc bromide, zinc carbonate, zinc chlorate, zinc chloride, zinc cyanide, zinc fluoride, zinc formate, zinc nitrate, zinc oxalate, zinc sulfate, sulfurous acid Zinc, zinc tartrate.

The M source is one or more of compounds of Mg, Ca, A1, and Zn, wherein

The Mg compound is: magnesium oxide, magnesium acetate, magnesium benzoate, magnesium carbonate, magnesium chlorate, magnesium chloride, magnesium chromate, magnesium formate, magnesium hydroxide, magnesium nitrate, magnesium oxalate, magnesium perchlorate, magnesium phosphate , magnesium sulfate, magnesium thiosulfate;

The Ca compound is: calcium oxide, calcium chloride, calcium acetate, calcium azide, calcium benzoate, calcium carbonate, calcium chlorate, calcium dihydrogen phosphate, calcium fluoride, calcium formate, calcium hydrogen phosphate, hydrogen Calcium oxide, calcium nitrate, calcium nitrite, calcium oxalate, calcium perchlorate, calcium permanganate, calcium phosphate;

The compound of A1 is: alumina, aluminum chloride, aluminum fluoride, aluminum nitrate, aluminum perchlorate, sulfuric acid Zinc cyanide, zinc fluoride, zinc formate, zinc nitrate, zinc oxalate, zinc sulfate, zinc sulfite, zinc tartrate. The R source is a compound of S, P or Si, wherein

The compound of S is: sulfuric acid, lithium sulfate;

The compound of P is: phosphorus pentoxide, phosphoric acid, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, diammonium phosphate, ammonium phosphate, ammonium hydrogen phosphate;

The compound of Si is: silica, lithium silicate, silicon oxysilane and its hydrolysis product;

The CN source is a compound containing carbon and nitrogen triple bonds, acrylonitrile, polyacrylonitrile, acetonitrile, phenylacetonitrile, adiponitrile, cyanide, hydrocyanic acid, sodium cyanide, potassium cyanide, and compounds containing carbon and nitrogen double bonds. Base, primary aldimine, secondary aldimine, primary ketimine, secondary ketimine, aldoxime, ketoxime, benzophenone oxime, carbonyl cyanide m-chlorophenylhydrazine, carbon-nitrogen Elemental compounds pyridine, pyridine, pyrrole, pyrrole, nitrobenzene, phenol (picric acid), trinitrotoluene, trinitroresorcin, nitroglycerin, nitrosobenzene, nitrosamine, aldehyde a mixture of hydrazine, ketone oxime, carbon simple substance or carbon-containing compound with nitrogen elemental or nitrogen-containing compound, one or more;

Carbon-containing compounds are organic carbon sources such as glucose, fructose, sucrose, maltose, sorbose, polyethylene glycol, polyvinyl alcohol, polyethylene, polypropylene, starch, cellulose and their esters, ethylene-epoxyethylene polymers or Polymer of furanol, citric acid, inorganic carbon source acetylene black, carbon nanotubes, carbon nanofibers, gas carbon source is acetylene, formamidine, acetamidine;

The nitrogen-containing compounds are nitric acid, nitrate, nitrous oxide, nitrogen monoxide, dinitrogen trioxide, nitrogen dioxide, dinitrogen tetroxide, and dinitrogen pentoxide. The nitrates are iron nitrate and lithium nitrate.

The mixing mode of the invention is solid phase mixing, the rotation speed is l-50000r/min, the time is 0.1-72h; or the liquid phase is mixed, the mass solid content is 1-99%, the solvent is water, ethanol or acetone, and the rotation speed is l-50000r/min. , time 0.1-72h, then dried at 70-400 ° C, 0.1-72h;

The solid phase mixing or the liquid phase mixing uses a mechanical agitator, a planetary ball mill, a stirring ball mill, and a machine Mechanical fusion machine, mixer mixing; mechanical mixer l-50000r/min, planetary ball mill l-500r/min, agitating ball mill l-1000r/min, mechanical fusion machine l-2000r/min, mixer l-1000r/min .

The precursor of the invention is placed in a planetary ball mill, agitating ball mill, a mechanical fusion, a pulverizing device, and the rotation speed is l-50000r/min, wherein the mechanical stirring is l-50000r/min, the planetary ball mill l-500r/min, the agitating ball mill l-1000r/ Min, mechanical fusion l-2000r/min, mixer l-1000r/min, time 0.1-72h, to obtain the refined precursor.

1. Mixing, according to the Li element, the elements of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn contained in M, M, Mg, Ca, Al, Zn elements, R of S , P or Si element, the ratio of the amount of the substance: 0<Li 3 : 0 M 2 : 0 M, <0.5 : 1 R 3, the Li source, the M source, the M' source and the R source are mixed to obtain a precursor ;

2. Put the precursor into a tube furnace, box furnace, rotary kiln, roller kiln or tunnel kiln, and carry out high temperature pyrolysis reaction under the protection of nitrogen, inert gas or reducing gas, at 0.8-18 °C. The heating rate of /min is raised from room temperature to 500-1100 °C, pyrolysis reaction is 1-72h, the CN source gas is charged during the pyrolysis reaction, and naturally cooled to room temperature to obtain CN/Li _x M _y M' _z (R0 ₄ _n ) is coated or doped with a carbonitride (CN) in the Li _x M _y M' _z (R0 ₄ ) _n type compound, and the mass of the carbonitride (CN ) is CN/ Li _x M _y M' _z

(R0 ₄ ) 0.1-30% of _n mass, where 0<x 3, 0^y^2, 0 z<0.5, ln 3, CN/ Li _x M _y M' _z (R0 ₄ ) _n is olivine Type structure or Nasicon structure;

The flow rate of the nitrogen gas, the inert gas or the reducing gas is 0.1-5000 L/min, the oxygen volume in the furnace is controlled to be 200 ppm or less, the inert gas is argon or helium, and the reducing gas is hydrogen, carbon monoxide or acetylene. , hyperthyroidism or acetaminophen;

The source gas flow rate of the CN source is 0.1-5000 L/min, and the volume of the CN source gas in the furnace is 0.1-90%; the CN source gas is the following in the gas phase state: the compound containing carbon and nitrogen triple bonds, acrylonitrile, polypropylene Alkenonitrile, acetonitrile, phenylacetonitrile, adiponitrile, cyanide, hydrocyanic acid, sodium cyanide, potassium cyanide, compound containing carbon-nitrogen double bond, Schiff base, primary aldimine, secondary aldimine, one Ketoimine, secondary ketimine, aldoxime, ketooxime, benzophenone oxime, carbonyl cyanide m-chlorophenylhydrazine, compound containing carbon and nitrogen, pyridine, pyridine, pyrrole, pyrrole, nitrobenzene , phenol (picric acid), trinitrotoluene, trinitroresorcin, nitroglycerin, nitrosobenzene, nitrosamines, aldoximes, ketoximes, carbon-containing compounds and nitrogen or nitrogen-containing compounds a mixture of more than one;

The carbon-containing compound is acetylene, formamidine, and ethyl hydrazine;

The nitrogen-containing compound is nitrous oxide, nitrogen monoxide, dinitrogen trioxide, nitrogen dioxide, and tetraoxide. The Li source of the present invention is lithium oxide, lithium hydroxide, lithium phosphate, lithium carbonate, lithium nitrate, and phosphoric acid. One or more of lithium hydrogen hydride, lithium formate and lithium acetate;

The compound of the Sc is: cerium oxide, cerium oxalate, cerium sulfate;

The Mn compound is: manganese oxide, manganese dioxide, manganese dioxide, trimanganese tetraoxide, manganese dimanganese oxide, manganese chloride, permanganate, manganese carbonate, potassium manganate, ammonium manganese sulfate, sulfurization Manganese, manganese acetate, manganese trifluoride, manganese tetrafluoride, manganese nitrate, manganese sulfate;

The Fe compound is: iron phosphate, ferrous sulfate, ferric oxide, ferrous oxide, triiron tetroxide, ammonium ferrous sulfate, ferrous sulfate, ferrous phosphate, ammonium ferrous phosphate, ferrous citrate Ferrocene, Ferrous sulphide, ferrous sulphide, ferrous acetate, ferric sulphate, ferric nitrate, ferrous chloride, ferric chloride, ferrous hydroxide, ferrous carbonate, ferrous nitrate, ferrous oxalate, ferrous perchlorate Iron hydroxide;

The Zn compound is: zinc oxide, zinc acetate, zinc bromide, zinc carbonate, zinc chlorate, zinc chloride, zinc cyanide, zinc fluoride, zinc formate, zinc nitrate, zinc oxalate, zinc sulfate, sulfurous acid Zinc, zinc tartrate; the M, the source is one or more of the compounds of Mg, Ca, A1 and Zn, wherein

The compound of A1 is: aluminum oxide, aluminum chloride, aluminum fluoride, aluminum nitrate, aluminum perchlorate, aluminum sulfate, aluminum hydroxide;

The Zn compound is: zinc oxide, zinc acetate, zinc bromide, zinc carbonate, zinc chlorate, zinc chloride, zinc cyanide, zinc fluoride, zinc formate, zinc nitrate, zinc oxalate, zinc sulfate, sulfurous acid Zinc, zinc tartrate; the R source is a compound of S, P or Si; The compound of the s is: sulfuric acid, lithium sulfate;

The compounds of Si are: silica, lithium silicate, bismuth silicon oxide and hydrolyzed products thereof.

The mixing device of the invention adopts mechanical stirring, planetary ball milling, agitating ball milling, mechanical fusion, mixing by a mixer; the mixing mode is solid phase mixing, liquid phase mixing, solid-liquid mixing;

The solid phase mixing speed is l-50000r/min, wherein the mechanical mixer l-50000r/min, the planetary ball mill l-500r/min, the agitating ball mill l-1000r/min, the mechanical fusion machine l-2000r/min, the mixer l- 1000r/min, time 0.1-72h;

The liquid phase mixing mass solid content is 1-99%, the solvent is water, ethanol or acetone, the rotation speed is l-50000r/min, wherein the mechanical stirring is l~50000r/min, the planetary ball grinding is l~500r/min, and the stirring ball mill l~ 1000r/min, mechanical fusion l~2000r/min, mixer l~1000r/min, time 0.1-72h, dry at 70-400 °C, 0.1-72h;

The solid-liquid mixing and mixing, first solid-phase mixing speed l-50000r/mm, wherein mechanical stirring l-50000r/min, planetary ball milling l-500r/min, stirring ball milling l-1000r/min, mechanical fusion l-2000r/min , Mixer l-1000r/min, time 0.1-72h; post-liquid phase mixing, mass solid content is 1-99%, solvent is water, ethanol or acetone, rotation speed l-50000r/min, mechanical stirring l-50000r/ Min, planetary ball mill l-500r/min, agitated ball mill l-1000r/min, mechanical fusion l-2000r/min, mixer l-1000r/min, time 0.1-72h, dry at 70-400 °C, 0.1- 72h.

The invention puts the precursor into the planetary ball mill, the agitating ball mill, the mechanical fusion, the pulverizing equipment, the rotation speed is l-50000r/min, wherein the mechanical stirring is l-50000r/min, the planetary ball mill l-500r/min, the agitating ball mill l-1000r/ Min, mechanical fusion l-2000r/min, mixer l-1000r/min, time 0.1-72h, to obtain the refined precursor. Compared with the prior art, the present invention uses a carbonitride compound as a coating or doping material to improve the conductivity of the electrode material, and the conductivity is superior to that of an electrode material coated or doped with a carbon material.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an XRD diagram of Embodiment 1 of the present invention.

Fig. 2 is an SEM image of Embodiment 1 of the present invention.

Fig. 3 is a graph showing the charge and discharge of a simulated battery of Example 1 of the present invention.

Fig. 4 is a graph showing the comparison of the 1C charge and discharge curves of the materials prepared in Example 1 of the present invention and Comparative Example 1.

Figure 5 is a sheet structure diagram of carbon.

Figure 6 is a structural diagram of a carbonitride compound.

detailed description

The present invention will be described in detail below with reference to the accompanying drawings and embodiments.

The positive electrode material of the present invention has the general formula CN/Li _x M _y M' _z (R0 ₄ ) _n and is coated or doped with a carbonitride CN in a Li _x M _y M' _z (R0 ₄ ) type compound. , the mass of CN is 0.1-30% of the mass of CN/Li _x M _y M' _z (R0 ₄ ) _n , where 0<x 3, 0 y 2, 0 z<0.5, ln 3, M is the periodic table of elements One or more of the elements Nos. 21 to 30, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, and M is one or more of Mg, Ca, Al, and Zn, and R is S. , P or Si. Among the coated or doped carbonitrides, carbon accounts for 1-99.9% of the elements, and nitrogen accounts for 0.01-70%. CN/Li _x M _y M' _z (R0 ₄ ) _n is an olivine structure or a Nasicon structure.

The CN source is a compound containing a carbon-nitrogen triple bond, a compound containing a carbon-nitrogen double bond, a compound containing a carbon-nitrogen element, a simple substance of carbon or a mixture of a carbon-containing compound and a nitrogen element or a nitrogen-containing compound, or more than one.

The carbon-nitrogen-containing triple bond compound is a nitrile, an isonitrile, or a cyanide: acrylonitrile, polyacrylonitrile, acetonitrile, phenylacetonitrile, adiponitrile, cyanide, hydrocyanic acid, sodium cyanide, potassium cyanide.

The compounds containing carbon and nitrogen double bonds are imines, anthraquinones, anthracenes: Schiff base, primary aldimine, secondary Aldimine, primary ketimine, secondary ketimine, aldoxime, ketoxime, benzophenone oxime, carbonyl cyanide m-chlorobenzene.

The carbon-nitrogen-containing compound is pyridine, pyridine, pyrrole, pyrrole, nitrobenzene, phenol (picric acid), trinitrotoluene TNT, trinitroresorcin (stringing acid), nitroglycerin, sub Nitrobenzene, nitrosamines, anthraquinones (aldoximes, ketoximes).

Carbon-containing compounds include organic carbon sources, inorganic carbon sources, and gaseous carbon sources. The organic carbon source is glucose, fructose, sucrose, maltose, sorbose, polyethylene glycol, polyvinyl alcohol, polyethylene, polypropylene, starch, cellulose and its esters, ethylene-epoxyethylene polymer or furanol. Polymer, citric acid. The inorganic carbon source is acetylene black, carbon nanotubes, and carbon nanofibers. The gas carbon source is acetylene, formamidine, and acetamidine.

The first method for synthesizing the positive electrode material of the present invention comprises the following steps:

1. Mixing, according to the Li element, the elements of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn contained in M, M, Mg, Ca, Al, Zn elements, R of S , P or Si element, the ratio of the amount of the substance: [0<Li 3] : [0 M 2] : [0 M, <0.5] : [1 R 3], CN source accounts for Li source, M source, M The source, the R source, and the source material of the CN source are 0.1-60% of the total mass, and the Li source, the M source, the M source, the R source, and the CN source are mixed to obtain a precursor.

The Li source is at least one of lithium oxide, lithium hydroxide, lithium phosphate, lithium carbonate, lithium nitrate, lithium dihydrogen phosphate, lithium formate and lithium acetate.

The M source is one or more of a simple substance or a compound of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn. among them, Titanium fluoride, titanium trioxide, titanium oxysulfate.

The compounds of V are: vanadium pentoxide, vanadium trioxide, vanadium dioxide and vanadium pentoxide.

The compounds of Cr are: chromium oxide, chromium nitrate, chromium perchlorate, and chromium sulfate.

The compounds of Mn are: manganese oxide, manganese dioxide, manganese dioxide, trimanganese tetraoxide, manganese dimanganese oxide, manganese chloride, permanganate, manganese carbonate, potassium manganate, manganese ammonium sulfate, manganese sulfide, Manganese acetate, manganese trifluoride, manganese tetrafluoride, manganese nitrate, manganese sulfate.

Fe compounds are: iron phosphate, ferrous sulfate, ferric oxide, ferrous oxide, triiron tetroxide, ammonium ferrous sulfate, ferrous sulfate, ferrous phosphate, ammonium ferrous phosphate, ferrous citrate, two Ferrocene, ferrous sulfide, ferrous phosphide, ferrous acetate, ferric sulphate, ferric nitrate, ferrous chloride, ferric chloride, ferrous hydroxide, ferrous carbonate, ferrous nitrate, ferrous oxalate, high chloride Ferrous acid, iron hydroxide.

The compounds of Co are: cobalt oxide, cobalt bromate, cobalt bromide, cobalt chlorate, cobalt chloride, cobalt fluoride, cobalt nitrate, cobalt nitrite, cobalt perchlorate, cobalt sulfate.

The compounds of Ni are: nickel oxide, nickel carbonate, nickel chlorate, nickel chloride, nickel fluoride, nickel nitrate, nickel perchlorate, nickel pyrophosphate, nickel sulfate.

The compounds of Cu are: copper oxide, cuprous chloride, cuprous cyanide, cuprous sulfide, cuprous thiocyanate, copper carbonate, copper chlorate, copper chloride, copper fluoride, copper formate, copper hydroxide, Copper nitrate, copper perchlorate, copper sulfate, copper sulfide.

The Zn compounds are: zinc oxide, zinc acetate, zinc bromide, zinc carbonate, zinc chlorate, zinc chloride, zinc cyanide, zinc fluoride, zinc formate, zinc nitrate, zinc oxalate, zinc sulfate, zinc sulfite, Zinc tartrate.

M, the source is one or more of compounds of Mg, Ca, A1 and Zn. among them,

The compounds of Mg are: magnesium oxide, magnesium acetate, magnesium benzoate, magnesium carbonate, magnesium chlorate, magnesium chloride, magnesium chromate, magnesium formate, magnesium hydroxide, magnesium nitrate, magnesium oxalate, magnesium perchlorate, magnesium phosphate, sulfuric acid Magnesium, magnesium thiosulfate. Ca compounds are: calcium oxide, calcium chloride, calcium acetate, calcium azide, calcium benzoate, calcium carbonate, calcium chlorate, calcium dihydrogen phosphate, calcium fluoride, calcium formate, calcium hydrogen phosphate, calcium hydroxide , calcium nitrate, calcium nitrite, calcium oxalate, calcium perchlorate, calcium permanganate, calcium phosphate.

The compound of A1 is: alumina, aluminum chloride, aluminum fluoride, aluminum nitrate, aluminum perchlorate, aluminum sulfate, aluminum hydroxide.

The source of R is a compound of S, P or Si. among them,

The compounds of S are: sulfuric acid, lithium sulfate.

The compounds of P are: phosphorus pentoxide, phosphoric acid, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate.

The compounds of Si are: silica, lithium silicate, bismuth silicon oxide and its hydrolysis products.

The compounds containing carbon and nitrogen double bonds are imines, anthraquinones, anthracenes: Schiff base, primary aldimine, secondary aldimine, primary ketimine, secondary ketimine, aldoxime, ketone Bismuth, benzophenone oxime, carbonyl cyanide m-chlorobenzene.

Carbon-nitrogen-containing compounds pyridine, pyridine, pyrrole, pyrrole, nitrobenzene, phenol (picric acid), trinitrotoluene TNT, trinitroresorcin (stringing acid), nitroglycerin, nitrosamine Benzobenzene, nitrosamines, anthraquinones (aldoximes, ketoximes).

Carbon-containing compounds include organic carbon sources, inorganic carbon sources, and gaseous carbon sources. The organic carbon source is glucose and fruit. Sugar, sucrose, maltose, sorbose, polyethylene glycol, polyvinyl alcohol, polyethylene, polypropylene, starch, cellulose and its esters, ethylene-epoxyethylene polymer or polymer of furanol, citric acid. The inorganic carbon source is acetylene black, carbon nanotubes, and carbon nanofibers. The gas carbon source is acetylene, formamidine, and acetamidine.

The mixing is carried out using a mechanical mixer, a planetary ball mill, a stirring ball mill, a mechanical fusion machine, and a mixer. The mixing method is solid phase mixing and liquid phase mixing.

Solid phase mixing speed l-50000r/min, including mechanical mixer l-50000r/min, planetary ball mill l-500r/min, agitating ball mill l-1000r/min, mechanical fusion machine l-2000r/min, mixer l-1000r/ Min, time 0.1-72h.

The liquid phase mixing mass solid content is 1-99%, the solvent is water, ethanol or acetone, the rotation speed is l-50000r/min, wherein the mechanical mixer l-50000r/min, the planetary ball mill l-500r/min, the agitating ball mill l-1000r/ Min, mechanical fusion machine l-2000r/min, mixer l-1000r/min, time 0.1-72h, dried at 70-400 ° C, 0.1-72h.

Second, refinement, the precursor into the planetary ball mill, mixing ball mill, mechanical fusion, crushing equipment, speed l-50000r / min, which mechanical stirring l-50000r / min, planetary ball mill l-500r / min, stirring ball mill l -1000r/min, mechanical fusion l-2000r/min, mixer l-1000r/min, time 0.1-72h, to obtain the refined precursor. The refinement process may not be performed.

3. Put the precursor or refined precursor into a tube furnace, box furnace, rotary kiln, roller kiln or tunnel kiln, and perform high temperature pyrolysis reaction under the protection of nitrogen, inert gas or reducing gas. , the temperature is raised from room temperature to 500-1100 °C at a heating rate of 0.8-18 ° C / min, pyrolysis reaction l-72 h, the furnace is naturally cooled to room temperature to obtain CN / Li _x M _y M' _z (R0 ₄ ) No In the Li _x M _y M' _z (R0 ₄ ) _n type compound, coated or doped with carbonitride CN, the mass of CN is 0.1/ mass of CN/ Li _x M _y M' _z (R0 ₄ ) _n 30%, Where 0<x 3, 0^y^2, 0 z<0.5, ln 3, M is the elements of the periodic table 21-30, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, One or more of Zn, M, is one or more of Mg, Ca, Al, and Zn, and 1 is 8, P or Si. CN/ Li _x M _y M' _z (R0 ₄ ) _n is an olivine structure or a Nasicon structure.

The flow rate of nitrogen, inert gas or reducing gas is 0.1~5000L/min, and the oxygen volume in the control furnace is below 200ppm. The inert gas is argon or helium. The reducing gas is hydrogen, carbon monoxide, acetylene, formamidine or acetamidine.

Because the organic carbon source has a carbon content of less than 50%, such as glucose, and the carbon content is 40%, the "CN source precursor accounts for 0.1-60% of the total mass of the material" undergoes a high temperature pyrolysis reaction, leaving a portion Carbon and nitrogen, other substances are decomposed, leaving 0.1-30%.

The second method for synthesizing the positive electrode material of the present invention comprises the following steps:

1. Mixing, according to the Li element, the elements of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn contained in M, M, Mg, Ca, Al, Zn elements, R of S , P or Si element, the ratio of the amount of the substance: [0<Li 3] : [0 M 2] : [0 M, <0.5] : [1 R 3], Li source, M source, M, source Mix with the R source to obtain a precursor.

The M source is one or more of a simple substance or a compound of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn. among them,

The compounds of Sc are: cerium oxide, cerium oxalate, cerium sulfate.

The compounds of ruthenium are: titanium dioxide, titanium tetrachloride, titanium trichloride, metatitanic acid, titanium dicarbonyl titania, titanium fluoride, titanium oxynitride, titanyl sulfate.

The compounds of V are: vanadium pentoxide, vanadium trioxide, vanadium dioxide and vanadium pentoxide. The compounds of Cr are: chromium oxide, chromium nitrate, chromium perchlorate, and chromium sulfate.

M, the source is one or more of compounds of Mg, Ca, A1 and Zn. among them,

The compounds of Mg are: magnesium oxide, magnesium acetate, magnesium benzoate, magnesium carbonate, magnesium chlorate, magnesium chloride, magnesium chromate, magnesium formate, magnesium hydroxide, magnesium nitrate, magnesium oxalate, magnesium perchlorate, magnesium phosphate, sulfuric acid Magnesium, magnesium thiosulfate.

Ca compounds are: calcium oxide, calcium chloride, calcium acetate, calcium azide, calcium benzoate, calcium carbonate, calcium chlorate, calcium dihydrogen phosphate, calcium fluoride, calcium formate, calcium hydrogen phosphate, calcium hydroxide , calcium nitrate, nitrous oxide Calcium acid, calcium oxalate, calcium perchlorate, calcium permanganate, calcium phosphate.

The source of R is a compound of S, P or Si. among them,

The compounds of S are: sulfuric acid, lithium sulfate.

The mixing equipment is mechanically agitated, planetary ball milled, agitated ball mill, mechanically blended, and mixer blended. The mixing method is solid phase mixing, liquid phase mixing, and solid-liquid mixing.

The liquid phase mixing mass solid content is 1-99%, the solvent is water, ethanol or acetone, the rotation speed is l-50000r/min, wherein the mechanical stirring is l~50000r/min, the planetary ball milling is l~500r/min, and the agitating ball milling l~1000r/ Min, mechanical fusion l~2000r/min, mixer l~1000r/min, time 0.1-72h, dry at 70-400 °C, 0.1-72h.

Solid-liquid mixing, first solid-phase mixing speed l-50000r/min, mechanical stirring l-50000r/min, planetary ball mill l-500r/min, agitating ball mill l-1000r/min, mechanical fusion l-2000r/min, mixing Machine l-1000r/min, time 0.1-72h. After liquid phase mixing, the mass solid content is 1-99%, the solvent is water, ethanol or acetone, the rotation speed is l-50000r/min, wherein the mechanical stirring is l-50000r/min, the planetary ball milling is l-500r/min, Stir ball mill l-1000r/min, mechanical fusion l-2000r/min, mixer l-1000r/min, time 0.1-72h, dry at 70-400 ° C, 0.1-72h.

Second, refinement, the precursor into the planetary ball mill, mixing ball mill, mechanical fusion, crushing equipment, speed l-50000r / min, which mechanical stirring l-50000r / min, planetary ball mill l-500r / min, stirring ball mill l -1000r/min, mechanical fusion l-2000r/min, mixer l-1000r/min, time 0.1-72h, to obtain the refined precursor. More fine reactants are obtained to make the chemical reaction more complete. The refinement process may not be performed.

3. Put the precursor or refined precursor into a tube furnace, box furnace, rotary kiln, roller kiln or tunnel kiln, and perform high temperature pyrolysis reaction under the protection of nitrogen, inert gas or reducing gas. The temperature is raised from room temperature to 500-1100 °C at a heating rate of 0.8-18 ° C / min, pyrolysis reaction l-72 h, charged with CN source gas during pyrolysis reaction, and naturally cooled to room temperature to obtain CN/Li _x M _y M' _z (R0 ₄ ) _n . At Li _x M _y M' _z

(!^^ type compound is coated or doped with carbonitride CN, the mass of CN is 0.1-30% of the mass of CN/ Li _x M _y M' _z (R0 ₄ ) _n , where 0<x 3, 0 y 2, 0 z<0.5, ln 3, M is one or more of elements Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn of No. 21-30 of the periodic table, M, It is one or more of Mg, Ca, Al, and Zn, and R is S, P, or Si. CN/ Li _x M _y M' _z (R0 ₄ ) _n is an olivine structure or a Nasicon structure.

The flow rate of nitrogen, inert gas or reducing gas is 0.1-5000 L/min, and the oxygen volume in the controlled furnace is below 200 ppm. The inert gas is argon or helium. The reducing gas is hydrogen, carbon monoxide, acetylene, formamidine or acetamidine.

The source gas flow rate of the CN source is 0.1-5000 L/min, and the volume of the CN source gas in the controlled furnace is 0.1-90%.

The CN source gas is one or more of a nitrile-based or cyanide-containing carbon-nitrogen triple bond compound, and one or more of the imine-based carbon-nitrogen double bond-containing compounds, other carbon-nitrogen-containing organic compounds and compounds, and carbon simple substance. Or a mixture of a carbon-containing compound or organic substance and a nitrogen element or a nitrogen-containing compound or a nitrogen-containing organic substance. Specific gas phase The following substances in the state:

Carbon-nitrogen triple bond-containing compound acrylonitrile, polyacrylonitrile, acetonitrile, phenylacetonitrile, adiponitrile, cyanide, hydrocyanic acid, sodium cyanide, potassium cyanide, compound containing carbon and nitrogen double bond, Schiff base, first grade Aldimine, secondary aldimine, primary ketimine, secondary ketimine, aldoxime, ketoxime, benzophenone oxime, carbonyl cyanide m-chlorophenylhydrazine, compound pyridine containing carbon and nitrogen elements, Pyridines, pyrrole, pyrrole, nitrobenzene, phenol (picric acid), trinitrotoluene, trinitroresorcin, nitroglycerin, nitrosobenzene, nitrosamines, aldoxime, ketoxime, a mixture of a carbon-containing compound (gas carbon source) and a nitrogen element or a nitrogen-containing compound, one or more of which;

The gas carbon source is acetylene, formamidine, and acetamidine;

Nitrogen-containing compounds are nitrous oxide, nitric oxide, dinitrogen tetroxide, nitrogen dioxide, and tetraoxide. Because of the organic carbon sources listed, the carbon content is mostly below 50%, so "the CN source precursors account for the total material quality." 0.1-60% "After high temperature pyrolysis, leaving some carbon and nitrogen, the other substances are decomposed, leaving 0.1-30%.

The positive electrode material prepared by the method of the present invention is observed by PANalytica X' PERT PRO X-ray diffractometer (Netherlands) CN/Li _x M _y M' _z (R0 ₄ ) _n is an olivine structure or a Nasicon structure, using American PE An atomic emission spectrometer of Platinum Elmer Optima 2100DV was observed to coat or be doped with a carbonitride CN in a Li _x M _y M' _z (R0 ₄ ) ₁₁ type compound. The conductivity of the positive electrode material was tested using a FZ-9601 four-probe powder resistivity tester from Shanghai Hongyun Testing Instrument Co., Ltd.

The process parameters of Examples 1-8 are shown in Table 1.

The positive electrode material of Example 1-8, acetylene black, and the binder mass ratio of 90:5:5, respectively, were mixed and applied to an aluminum foil to serve as a positive electrode for the simulated battery. The negative electrode is a lithium metal plate, the separator is Cel _ga rd2400, and the electrolyte is 1 mol/L LiPF ₆ /DMC+DEC (volume ratio of 1:1), and assembled into a CR2025 type analog battery. In On the CT-3008w-5V10mA-Sl battery detection system of Shenzhen Xinwei Battery Testing Equipment Co., Ltd., the charging and discharging cycle of the analog battery, voltage 2.5-3.9V, current 0.1-1C, test its charging and discharging performance and capacity, test The results are shown in Table 2. The process parameters of Comparative Example 1 are shown in Table 1. The positive electrode materials of Comparative Example 1 were assembled into CR2025 type analog batteries in the same manner as above, and the charge and discharge performance and capacity were tested according to the same test method as in Example 1-8. The test results are shown in Table 2.

As shown in Fig. 1, an XRD pattern of the positive electrode material prepared in Example 1 was obtained by using a graphite monochromator, Cu leather Ε (λ = 0.15406 nm), a scanning speed of 10 min, and a scanning range of 10 ° to 90 °. The figure is compared with the XRD standard spectrum (Reference code: 01-081-1173), which is an olivine structure.

As shown in Fig. 2, the scanning electron microscope showed that the positive electrode material particles prepared in Example 1 were between 100 nm and lum.

As shown in Fig. 3, the half-cell charge and discharge platform prepared by the method of the invention as a positive electrode is stable, has small electrochemical polarization, and has a capacity of 156 mAh/g. As shown in FIG. 4, the 1C charge-discharge curve of Comparative Example 1 was compared with the 1C charge-discharge curve of Example 1, and the discharge voltage platform using CN/LiFeP0 ₄ material was higher, and the specific capacity of Example 1 was 145 mAh/g. The specific capacity of Comparative Example 1 was 139 mAh/g. Table 1 Process parameters of Examples 1-8 and Comparative Example 1

Example or comparison Step 1 Niu Congyi Step 3 Results

Example 1, coated or lithium carbonate, dihydrogen phosphate plus acrylonitrile-containing material, the dry material is placed to obtain an olivine-type doped with ammonium carbonitride, iron oxide, the percentage of massage amount is into the box furnace, CN /LiFeP0 ₄ , CN total lithium iron phosphate material ratio 1: 2: 1, adding 30% of the emulsion, the milk is nitrogen, the flow rate is 1.7%, wherein the CN/LiFeP0 ₄ alcohol makes the solid content 5%, N, the liquid content of all raw materials 2L / min, C content of 1. 5%, N 2%, the content of the mass percentage of 0. 2%

The speed of the ball at room temperature is 5%, placed at the ball mill rate, and the temperature is raised.

Grinding for 8 hours, ball milling in the tank 2 small 700 °C, sintering 6

When the speed is hour

70r/min. take out

Material is dry, true

Drying in an empty drying oven

Dry, 120 "C,

10h.

Example 2, coating or the same as Example 1 with acrylonitrile-containing material as in Example 1 to obtain an olivine-type doped carbonitride content of CN/LiFeP0 ₄ , CN total of lithium iron phosphate 30% The emulsion has a milk content of 30%, wherein the C material CN/LiFeP0 ₄ liquid accounts for 28% of all raw materials, and the N content mass percentage is 2%.

mouth

60%, placed in a ball mill

Ball mill in the tank 2 small

When the speed is

70r/min. take out

Material is dry, true

Drying in an empty drying oven

Dry, 120 degrees,

10h.

Example 3, coating or the same as Example 1 with acrylonitrile-containing material as in Example 1 to obtain an olivine-type doped with a carbonitride content of CN/LiFeP0 ₄ , CN total of lithium iron phosphate 30% emulsion, milk content of 0.1%, wherein the feed CN / LiFeP0 ₄ cent of all liquid material the C content is 0. 09%, N

01%,

0. 5%, placed on the ball

Grinding can ball mill 2

Hour, the speed is

70r/min. take out Material is dry, true

Drying in an empty drying oven

Dry, 120 degrees,

10h.

Example 4, coating or the same as in the first embodiment, the dry material is not put into the olivine-type doped carbonitride-incorporated tube furnace, CN/LiFeP0 ₄ , the material of the lithium iron phosphate material is passed through the nitrogen, the flow rate

Material CN/LiFeP0 ₄ 0.6L/min, to

5 ° C / min speed

Rate rises to

700 °C, insulation 6

Hour, cyanide

Volume ratio to nitrogen

For a 2: 1 mix

Gas, gas flow

control in

0.5 L/min. Self

Cool down

Example 5, coating or lithium acetate, oxalic acid sub-transfer to the planetary ball ethanol volatilization, the olivine-type doped with carbonitride, iron silicate, grinding, adding benzene to put the material into the box CN / Li ₂ FeSi0 ₄ , lithium iron silicate material 2:1:1 ratio, force acetonitrile, in the forehearth furnace, nitrogen

Inject anhydrous ethanol to 2% of the solid mass, gas protection,

The content is 30%, and it is added to the ball mill for 24 hours. Vacuum mechanical stirring at 2 ° C / min, to increase the drying rate in the drying oven to

Drying at 1500r/min, 70°C, 10h. 650 ° C, sintering 24

Speed, stirring 2h,, hours, natural drop

曰〉, 曰

Example 6, coating or lithium acetate, manganese acetate, adding solid matter, drying the material to obtain olivine-type CN/LiFeMnP0 in a roller furnace kiln doped with carbonitriding iron oxide and phosphoric acid 2% by mass ₄ , the substance of iron manganese hydride lithium hydrogen phosphate, molar ratio of glucose, propylene for sintering, nitrogen

Material 1: 0.5:0.5:1, gas-protected with a mass percentage of nitrile, sintered 200r/min speed, 40% emulsion, temperature 550 ° C, 30

Stir the ball mill at room temperature 5 The entire emulsion takes up the hour.

Hour, there are raw materials quality

1% of the score, plus

Stir in ethanol

2h, water bath heating

Stirring and drying 90 degrees

5h.

Example 7. Coating or lithium hydroxide, pentoxide, adding acrylonitrile, drying the material, and then obtaining the NASICON structure into the tube furnace.

Doped with vanadium carbonitride, CN/ Li ₃ V ₂ (P0 ₄ )3 with a mass percentage of dihydrogen phosphate, sintered, nitrogen

Lithium vanadium phosphate material ammonium, in a molar ratio of 30% emulsion, integral protection, sintering temperature

Degree 850 °C, 20

Material 3 : 1 : 3 , with a lot of emulsion

hour.

260r/min speed, raw material mass percentage

Stir the ball mill 5% at room temperature, add

Hour, ethanol is stirred for 2 hours,

Water bath heating and stirring

Dry at 180 ° C for 2 h.

Example 8, coating or lithium hydroxide, sulfuric acid Example 1 Same as Example 1 to obtain an olivine type doped with carbonitride, phosphoric acid, magnesium acetate, CN/LiFe _0. ₉₈ Mgo. ₀₂ P0 ₄ , the substance of lithium iron magnesium phosphate massage

Material 3 : 0. 98 : 1 : 0. 02 ,

CN/LiFe ₀ . ₉₈ Mgo. ₀₂ P0 ₄ plus ethanol to solid content

30% to

70r/min speed,

Ball milling at room temperature 8 small,

Comparative Example 1, coating or addition to Example 1 to the mixture of Example 1 to obtain an olivine-type carbon-doped phosphoric acid plus mass percentage C/LiFeP0 ₄ ,

Iron lithium material for 5% of grapes

Sugar, placed in a ball mill

Ball mill in the tank 2 small

When the speed is 70r/min. take out

Material drying Table 2 Examples 1-8 and Comparative Example 1 Electrical property test results

In the examples of the present invention, lithium carbonate, lithium hydroxide, lithium acetate in Li source, Li source not listed, and Li source listed in the examples are respectively provided to provide Li element in the chemical reaction process, and M The source, the M' source, and the R source are reacted and sintered to form Li _x M _y M' _z (R0 ₄ ) _n .

In the embodiment of the present invention, V, Mn, Fe in the M source are respectively used, and other elements not listed: Sc, Ti, Co, Ni, Cu, Zn, and V, Mn, Fe listed in the examples belong to The subgroup elements of the fourth cycle of the chemical periodic table can form an olivine structure or a Nasicon structure with Li and R04, or form a metal doping.

In the examples of the present invention, Mg in the M' source is respectively used, and other elements not listed: Ca, Al, Zn, and the same metal elements as the Mg listed in the examples, can form gold in the final product. Is doped.

In the examples of the present invention, P and Si in the R source are respectively used, and other elements not listed: S, which are the same as the P and Si enumerated in the examples, can form a compound in the form of R0 ₄ .

In the examples of the present invention, acrylonitrile, cyanogen, and phenylacetonitrile in the CN source are respectively used, and other CN sources not listed are used, and the acrylonitrile, cyanogen, and phenylacetonitrile listed in the examples are nitrogen-containing compounds or Carbonitrides, they form a complex or compound of C and N during pyrolysis.

As shown in FIG. 5, the prior art is to coat or dope with pure carbon to improve the conductivity of the material. The principle of conduction: In the carbon layer structure, each carbon atom is directly adjacent to the other three. Three carbon atoms form three. Covalently a single bond, then one electron of each carbon atom forms a large π bond with this electron of each of the other carbon atoms, and the electrons in the delocalized bond can move freely in this plane, so in this plane direction, Can be electrically conductive. The conductivity of carbon is mainly derived from the large π bond of SP2 hybridization.

As shown in Fig. 6, the present invention uses a carbonitride compound, which is more conductive than pure carbon, because of a carbonitride, a ruthenium element in a six-membered ring has a pair of lone pairs of electrons, and a large π bond with respect to a C element. In the middle, it contributes a free electron to obtain higher conductivity.

Claims

Claim

A positive electrode material, characterized in that: the positive electrode material of the formula _{_{CN / Li x M y M '}} z (R0 4) n, in _{_{_{Li x M y M' z (}}} R0 4) type compound ₁₁ The carbon-nitrogen compound (CN) is coated or doped. In the carbon-nitrogen compound, the ratio of carbon to the element is 1-99.9%, the proportion of nitrogen to the element is 0.01-70%, and the mass of the carbon-nitrogen compound is CN. /Li _x M _y M' _z (R0 ₄ ) _n 0.1-30% of mass, where 0<x 3, 0 y 2, 0 z<0.5, ln 3, M is an element Sc, Ti, V, Cr, One or more of Mn, Fe, Co, Ni, Cu, and Zn, M is one or more of Mg, Ca, Al, and Zn, and R is S, P or Si, CN/Li _x M _y M' _z (R0 ₄ ) _n is an olivine structure or a Nasicon structure;

The nitrogen-containing compound is nitric acid, nitrate, nitrous oxide, nitrogen monoxide, dinitrogen trioxide, nitrogen dioxide, dinitrogen tetroxide, dinitrogen pentoxide, and the nitrate is ferric nitrate or lithium nitrate.

2. A method for synthesizing a positive electrode material, comprising the following steps: 1. Mixing, according to the Li element, the elements of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn contained in M, M, Mg, Ca, Al, Zn elements, R of S , P or Si element, the ratio of the amount of the substance: 0<Li 3 : 0 M 2 : 0 M, <0.5 : 1 R 3, CN source accounts for Li source, M source, M, source, R source and CN source 0.1-60% of the total mass of the precursor material, mixing Li source, M source, M, source, R source and CN source to obtain a precursor;

2. Put the precursor into a tube furnace, box furnace, rotary kiln, roller kiln or tunnel kiln, and carry out high temperature pyrolysis reaction under the protection of nitrogen, inert gas or reducing gas, at 0.8-18 °C. The heating rate of /min is raised from room temperature to 500-1100 ° C, pyrolysis reaction l-72 h, and the furnace is naturally cooled to room temperature to obtain CN/ Li _x M _y M' _z (R0 ₄ ) _n , in Li _x M _y M' _z (R0 ₄ )! ! The compound is coated or doped with a carbonitride CN, and the mass of CN is 0.1-30% of the mass of CN/Li _x M _y M' _z (R0 ₄ ) _n , wherein 0<x 3, 0 y 2, 0 z<0.5, ln 3, CN/ Li _x M _y M' _z (R0 ₄ ) _n is an olivine structure or a Nasicon structure;

The method for synthesizing a positive electrode material according to claim 2, wherein the U source is lithium oxide, lithium hydroxide, lithium phosphate, lithium carbonate, lithium nitrate, lithium dihydrogen phosphate, lithium formate and acetic acid. More than one of lithium;

The compound of the Sc is: cerium oxide, cerium oxalate, cerium sulfate;

The ruthenium compound is: titanium dioxide, titanium tetrachloride, titanium trichloride, metatitanic acid, dicarbonyl titanocene, titanium fluoride, titanium oxynitride, titanyl sulfate; The compound of V is: vanadium pentoxide, vanadium pentoxide, vanadium dioxide and vanadium pentoxide; the compound of Cr is: chromium oxide, chromium nitrate, chromium perchlorate, chromium sulfate;

The Fe compound is: iron phosphate, ferrous sulfate, ferric oxide, ferrous oxide, triiron tetroxide, ammonium ferrous sulfate, ferrous sulfate, ferrous phosphate, ammonium ferrous phosphate, ferrous citrate , ferrocene, ferrous sulfide, ferrous phosphide, ferrous acetate, ferric sulphate, ferric nitrate, ferrous chloride, ferric chloride, ferrous hydroxide, ferrous carbonate, ferrous nitrate, ferrous oxalate, Ferrous perchlorate, iron hydroxide;

The Zn compound is: zinc oxide, zinc acetate, zinc bromide, zinc carbonate, zinc chlorate, zinc chloride, zinc cyanide, zinc fluoride, zinc formate, zinc nitrate, zinc oxalate, zinc sulfate, sulfurous acid Zinc, zinc tartrate; the M, the source is one or more of the compounds of Mg, Ca, A1 and Zn, wherein the Mg compound is: magnesium oxide, magnesium acetate, magnesium benzoate, magnesium carbonate, chloric acid Magnesium, magnesium chloride, magnesium chromate, magnesium formate, magnesium hydroxide, magnesium nitrate, magnesium oxalate, magnesium perchlorate, magnesium phosphate, magnesium sulfate, magnesium thiosulfate;

The compounds of Ca are: calcium oxide, calcium chloride, calcium acetate, calcium azide, calcium benzoate, carbon Calcium acid, calcium chlorate, calcium dihydrogen phosphate, calcium fluoride, calcium formate, calcium hydrogen phosphate, calcium hydroxide, calcium nitrate, calcium nitrite, calcium oxalate, calcium perchlorate, calcium permanganate, calcium phosphate;

The Zn compound is: zinc oxide, zinc acetate, zinc bromide, zinc carbonate, zinc chlorate, zinc chloride, zinc cyanide, zinc fluoride, zinc formate, zinc nitrate, zinc oxalate, zinc sulfate, sulfurous acid Zinc, zinc tartrate; the R source is a compound of S, P or Si, wherein

The compound of S is: sulfuric acid, lithium sulfate;

Carbon-containing compounds are organic carbon sources such as glucose, fructose, sucrose, maltose, sorbose, polyethylene glycol, polyvinyl alcohol, polyethylene, polypropylene, starch, cellulose and their esters, ethylene-epoxyethylene polymers or Polymer of furanol, citric acid, inorganic carbon source acetylene black, carbon nanotubes, carbon nanofibers, gas carbon source is acetylene, formamidine, acetamidine; Nitrogen, dinitrogen tetroxide, dinitrogen pentoxide, nitrate is ferric nitrate, lithium nitrate.

The method for synthesizing a positive electrode material according to claim 2, wherein the mixing mode is solid phase mixing, the rotation speed is 1-50000 r/min, and the time is 0.1-72 h; or the liquid phase is mixed, and the mass solid content is 1-99%, the solvent is water, ethanol or acetone, the rotation speed is -50000r/min, the time is 0.1-72h, and then dried at 70-400 °C for 0.1-72h;

The solid phase mixing or the liquid phase mixing is mixed by a mechanical agitator, a planetary ball mill, a stirring ball mill, a mechanical fusion machine, a mixer; the mechanical mixer l-50000r/min, a planetary ball mill l-500r/min, a stirring ball mill l-1000r /min, mechanical fusion machine l-2000r/min, mixer l-1000r/min.

The method for synthesizing a positive electrode material according to claim 2, wherein: the precursor is placed in a planetary ball mill, a stirred ball mill, a mechanical fusion, and a pulverizing apparatus, and the rotation speed is 1-50000 r/min, wherein the mechanical stirring is -50000r/min, planetary ball mill l-500r/min, agitated ball mill l-1000r/min, mechanical fusion l-2000r/min, mixer l-1000r/min, time 0.1-72h, to obtain the refined precursor.

6. A method for synthesizing a positive electrode material, comprising the following steps:

1. Mixing, according to the Li element, the elements of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn contained in M, M, Mg, Ca, Al, Zn elements, R of S , P or Si element, the ratio of the amount of the substance: 0 <Li 3 : 0 M 2 : 0 M, <0.5 : 1 R 3, the Li source, the M source, the M' source and the R source are mixed to obtain a precursor ;

(R0 ₄ ) 0.1-30% of _n mass, where 0<x 3, 0^y^2 , 0 z<0.5, ln 3, CN/ Li _x M _y M' _z (R0 ₄ ) _n is an olivine structure or a Nasicon structure;

The source gas flow rate of the CN source is 0.1-5000 L/min, and the volume of the CN source gas in the furnace is 0.1-90%; the CN source gas is the following in the gas phase state: a compound containing carbon and nitrogen triple bonds, acrylonitrile, polyacrylonitrile, Acetonitrile, phenylacetonitrile, adiponitrile, cyanide, hydrocyanic acid, sodium cyanide, potassium cyanide, compound containing carbon-nitrogen double bond, Schiff base, primary aldimine, secondary aldimine, primary ketone Amine, secondary ketimine, aldoxime, ketone oxime, benzophenone oxime, carbonyl cyanide m-chlorophenylhydrazine, compound containing carbon and nitrogen element pyridine, pyridine, pyrrole, pyrrole, nitrobenzene, phenol (picric acid), trinitrotoluene, trinitroresorcin, nitroglycerin, nitrosobenzene, nitrosamines, aldoximes, ketoximes, mixtures of carbon-containing compounds with nitrogen or nitrogen-containing compounds, More than one;

The carbon-containing compound is acetylene, formamidine, and ethyl hydrazine;

The nitrogen-containing compound is nitrous oxide, nitrogen monoxide, dinitrogen trioxide, nitrogen dioxide, and tetraoxane.

The method for synthesizing a positive electrode material according to claim 6, wherein the U source is lithium oxide, lithium hydroxide, lithium phosphate, lithium carbonate, lithium nitrate, lithium dihydrogen phosphate, lithium formate and acetic acid. More than one of lithium;

The compound of the Sc is: cerium oxide, cerium oxalate, cerium sulfate;

The Zn compound is: zinc oxide, zinc acetate, zinc bromide, zinc carbonate, zinc chlorate, zinc chloride, zinc cyanide, zinc fluoride, zinc formate, zinc nitrate, zinc oxalate, zinc sulfate, sulfurous acid Zinc, zinc tartrate; the R source is a compound of S, P or Si;

The compound of S is: sulfuric acid, lithium sulfate;

The method for synthesizing a positive electrode material according to claim 6, wherein the mixing device is mechanically stirred, planetary ball milled, stirred ball milled, mechanically fused, and mixed by a mixer; the mixed mode is solid phase mixing, liquid Mixed, solid-liquid mixing;

The solid-liquid mixing and mixing, first solid-phase mixing speed l-50000r/mm, wherein mechanical stirring l-50000r/min, planetary ball milling l-500r/min, stirring ball milling l-1000r/min, mechanical fusion l-2000r/min , Mixer l-1000r/min, time 0.1-72h; post-liquid phase mixing, mass solid content is 1-99%, solvent is water, ethanol or acetone, rotation speed l-50000r/min, mechanical stirring l-50000r/min , Planetary ball mill l-500r/min, agitated ball mill l-1000r/min, mechanical fusion l-2000r/min, mixer l-1000r/min, time 0.1-72h, 70-400°C, dry 0.1-72h .

9. The method for synthesizing a positive electrode material according to claim 6, wherein: the precursor is placed in a planetary ball mill, a stirred ball mill, a mechanical fusion, and a pulverizing apparatus, and the rotation speed is 1-50000 r/min, wherein the mechanical stirring l- 50000r/min, planetary ball mill l-500r/min, agitated ball mill l-1000r/min, mechanical fusion l-2000r/min, mixer l-1000r/min, time 0.1-72h, to obtain the refined precursor.