CN107742712B - A kind of conducting polymer coating-doping type anode material for lithium-ion batteries and its synthetic method - Google Patents

A kind of conducting polymer coating-doping type anode material for lithium-ion batteries and its synthetic method Download PDF

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CN107742712B
CN107742712B CN201711001514.9A CN201711001514A CN107742712B CN 107742712 B CN107742712 B CN 107742712B CN 201711001514 A CN201711001514 A CN 201711001514A CN 107742712 B CN107742712 B CN 107742712B
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lithium
conducting polymer
ion batteries
anode material
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CN107742712A (en
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陈召勇
龚小龙
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Changsha University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention discloses a kind of conducting polymer coating-doping type anode material for lithium-ion batteries and its synthetic method, and the general molecular formula of the anode material for lithium-ion batteries is aICP (1-a) Li1‑ xM1‑yMexM 'yO2‑zTz(0≤x≤0.05,0≤y≤0.05,0≤z≤0.05,0 < a≤0.1), wherein ICP be one of polypyrrole, polyphenylene sulfide, polyaniline, polythiophene or a variety of, M Mn, Ni, Co, Al, Cr, Mg, Ca, Zr, Ti, Zn, Fe it is one or more, Me, M` are metallic element, it is preferred that one of Na, K, Ba, Zn, Mg, T is halogens, preferably one of F, Cl, Br.Steps are as follows: first carrying out wet-milling with the additive of element containing Me and T element, lithium source, transition metal precursor, dries, then roasting obtains doped samples, then is coated with conducting polymer to doped samples.The doped conductivity for coating obtained sample and improving material, inhibits erosion of the electrolyte to material, and rate capability improves significantly, is suitable for lithium ion battery.

Description

A kind of conducting polymer coating-doping type anode material for lithium-ion batteries and its synthesis Method
Technical field
The invention belongs to anode material for lithium-ion batteries and its preparation technical field, a kind of conductive polymer modified doping type Anode material for lithium-ion batteries and its synthetic method.
Background technique
With the continuous consumption of petroleum resources, the crude resources that can be used is fewer and fewer, in the near future, petroleum money The depleted of source is inevitable.So in order to reduce the use to petroleum resources as far as possible, many countries and science and technology All strongly promoting electric car and hybrid vehicle in field.On the one hand the use to petroleum resources, another party can be reduced Face can also reduce car tail gas and discharge brought problem of environmental pollution.Lithium ion battery has high-energy-density, environmental pollution The features such as small, memory-less effect, high security, achieves in fields such as laptop, mobile communication, small type mobile devices Considerable achievement establishes lithium ion battery unrivaled advantage in various battery systems, and is highly suitable for mixing Close power vehicle, electric car field.It is pointed out according to correlative study analysis, using lithium-ion-power cell as hybrid vehicle Power supply device, effective utility of laser power may be up to 90%.Therefore, high-energy, novel high-power, high safety are researched and developed Property lithium ion battery will become energy and material developmental research one of important goal.
In numerous secondary cell systems, lithium ion battery is because of high-energy-density, environmental-friendly, memory-less effect and depth It is studied by everybody.But these materials there is also many problems have it is to be solved.(1) ionic conductivity of material is relatively low, ion Diffusion coefficient is low, poor so as to cause high rate performance.(2) thermal stability of material is poor.(3) interface stability of material is poor, It is easy to be corroded by electrolyte.(4) stability is poor under high voltages for material.
Then the present invention carries out the cladding of conducting polymer to it to improve again by being first doped to lithium ion battery The above problem, doped alkali metal ion expand lithium ion transport channel to improve the conductivity of material, inhibit cationic mixing Phenomenon.It is coated with macromolecule conducting material to improve the interface stability of material, is inhibited by electrolytic corrosion.The present invention adopts Take vapour deposition process in positive electrode surface coated with conductive macromolecule, simple process has by positive electrode prepared by this method Effect improves its chemical property.
Summary of the invention
Problem to be solved by this invention is to provide a kind of conducting polymer coating-doping type anode material for lithium-ion batteries And its synthetic method, this method effectively inhibit the cationic mixing phenomenon of nickel-rich positive pole material, improve interface stability, Ionic conductivity is improved, to improve the chemical property of anode material for lithium-ion batteries.
To achieve the goals above, the present invention is implemented by following scheme:
A kind of conducting polymer coating-doping type anode material for lithium-ion batteries, general formula are aICP (1-a) Li1- xM1-yMexM′yO2-zTz(0≤x≤0.05,0≤y≤0.05,0 < z≤0.05,0 a≤0.1 <), wherein ICP is polypyrrole, gathers One of diphenyl sulfide, polyaniline, polythiophene are a variety of, M Mn, Ni, Co, Al, Cr, Mg, Ca, Zr, Ti, Zn, Fe it is any One or more, Me, M ' are metallic element, and preferably one of Na, K, Ba, Zn, Mg, T are halogens, preferably F, Cl, Br One of.
For example following step of synthetic method of the anode material for lithium-ion batteries of above-mentioned first doping, rear conducting polymer cladding It is rapid:
A. the additive of presoma, lithium source, the element containing Me and T is added in ball grinder, the mass percentage of additive Be 0.5%~10%, and a certain amount of solvent be added, with material ball ratio 1: 4~1: 20 carry out ball milling, rotational speed of ball-mill be 400~ 2000rpm, time are 2~16h；
B. the sample after ball milling is put into that drying box is dry, and drying temperature is 60~180 DEG C, and the time is 4~for 24 hours, grinding is equal After even 750~900 DEG C of 5~20h of heat treatment to get arrive doped lithium ion battery positive electrode sample；
C. obtained doped samples are added in distilled water, a certain proportion of surfactant, oxidant is successively added Enter and wherein stir certain time, then filter, dry, drying temperature is 60~180 DEG C, and the time is 8h~20h；
D. the sample of drying is placed in closed container, then is put into conductive polymer material in closed container, it is conductive high The quality of molecular material is the 1%~10% of sample quality, and is in certain proportion with surfactant, the oxidant in step c, By conductive polymer material in 60 DEG C~180 DEG C heated at constant temperature 2h~for 24 hours, the lithium ion anode material of conducting polymer cladding is obtained Material.
In step a, the presoma is precursor of lithium ionic cell positive material, is hydroxide precursor, carbonic acid Salt precursor body, oxalate precursor, bicarbonate presoma, hydroxyl groups precursors；The lithium source be lithium carbonate, lithium hydroxide, The combination of one or more of lithium nitrate, lithium oxalate, lithium dihydrogen phosphate, lithium chloride.
In step a, the metallic element Me is alkali metal element, alkali earth metal, the 13rd race's element, the 14th race member One of element, transition element, preferably containing one of sodium, potassium, aluminium, magnesium, the oxide of barium, hydroxide, carbonate；Institute The element T stated is selected from one of halogens, one of preferably fluorine-containing, chlorine, bromine substance
In step a, the solvent is the combination of one or more of ethyl alcohol, distilled water, methanol, acetone.
In step c, the surfactant is benzene sulfonic acid sodium salt, Riboflavine sodium phosphate, polyethylene glycol, one in stearic acid Kind or a variety of combinations；The oxidant is one of sodium thiosulfate, potassium thiosulfate, ATS (Ammonium thiosulphate).
In step c, the ratio of the surfactant and oxidant is 5:1~1:5；The mixing time is 10min~120min.
In step d, the conductive polymer material be one of polypyrrole, polyaniline, polyphenylene sulfide, polythiophene or It is a variety of；The mass ratio of the conductive polymer material and surfactant is 1: 1~1: 100, conductive polymer material and oxygen The mass ratio of agent is 1: 1~1: 100.
The present invention is combined using solid phase method and vapour deposition process, is had the advantage that
(1) stability and conductivity that lithium ion battery material is mentioned using doping, also inhibit the mixing of cation Phenomenon.
(2) conducting polymer is coated on using vapour deposition process the surface of the anode material for lithium-ion batteries after doping, Improve the high rate performance and cyclical stability of anode material for lithium-ion batteries, it is suppressed that erosion of the electrolyte to material.
Detailed description of the invention
Fig. 1 is the doping of NaCl obtained by embodiment 1, polypyrrole surface cladding LiNi0.5Co0.2Mn0.3O2Positive electrode XRD diagram；
Fig. 2 is the doping of NaCl obtained by embodiment 1, polypyrrole surface cladding LiNi0.5Co0.2Mn0.3O2Positive electrode with And the LiNi of comparative example synthesis0.5Co0.2Mn0.3O20.1C first charge-discharge curve graph；
Fig. 3 is the doping of NaCl obtained by embodiment 1, polypyrrole surface cladding LiNi0.5Co0.2Mn0.3O2Positive electrode with And the LiNi of comparative example synthesis0.5Co0.2Mn0.3O21C cyclic curve figure；
Fig. 4 is the doping of NaCl obtained by embodiment 1, polypyrrole surface cladding LiNi0.5Co0.2Mn0.3O2Positive electrode with And the LiNi of comparative example synthesis0.5Co0.2Mn0.3O2Curve of double curvature figure；
Fig. 5 is that KCl obtained by embodiment 6 adulterates LiNi0.5Co0.2Mn0.3O2The 1C cyclic curve figure of positive electrode；
Fig. 6 is that KCl obtained by embodiment 6 adulterates LiNi0.5Co0.2Mn0.3O2The curve of double curvature figure of positive electrode
Specific embodiment
The invention will be further described with reference to embodiments.
Embodiment 1
Ni is weighed respectively0.5Co0.2Mn0.3(OH)2For 9.2524g, LiOHH2O is 3.3874g, Li2CO3For 0.9282g And NaCl is 0.587g, is put it into the ball grinder of the dehydrated alcohol equipped with 17mL, adds zirconium ball, material ball ratio 1:6, With 400rpm ball milling 4h, 60 DEG C of air dry oven dry 4h are placed, 6g is weighed and is put into 480 DEG C of pre-burning 3h of resistance box, 880 DEG C of calcinings 12h, heating rate are 5 DEG C/min, obtain sample.Sample 3g after weighing NaCl doping, is dissolved in the beaker equipped with distilled water, It is placed on magnetic stirring apparatus, stirs 30min, then surfactant propanesulfonate 1.74g is added into beaker, after stirring 10min, Then oxidant sodium thiosulfate 1.88g is added, after stirring 10min, is cleaned, is filtered, be put into 60 DEG C of constant temperature of air dry oven Dry 12h, the sample of drying is placed on the filter paper in culture dish, then is put one in culture dish and be equipped with polypyrrole 0.06g's In aluminium foil capsule, the amount of conductive polymer material is the 2% of sample quality, is sealed with preservative film, is placed in true dry 60 in drying box It is DEG C dry for 24 hours, obtain a kind of doped lithium ion positive electrode of conducting polymer cladding.
The assembling of battery: weighing the resulting lithium ion anode material of 0.4g, and 0.05g conductive carbon black (Super-P) is added and makees Conductive agent and 0.05g PVDF (HSV900) make binder, and 0.8g NMP dispersion mixing is added after being fully ground, after sizing mixing uniformly It is diaphragm, 1mol/L with Celgard 2300 using metal lithium sheet as cathode in anaerobism glove box in slurry film-making on aluminium foil LiPF6/ EC: DMC: EMC (volume ratio 1: 1: 1) is electrolyte, is assembled into the button cell of CR2025, enterprising in blue electric tester Row test, test voltage range are 2.7V~4.6V, and discharge capacity is 236.4mAh g for the first time-1, capacity is after 1C is recycled 100 times 171.6mAh g-1, capacity retention ratio 88.7%, capacity is also 177mAh g respectively under 3C, 5C-1、159.5mAh g-1, remote high In unmodified sample.
Embodiment 2
Ni is weighed respectively0.5Co0.2Mn0.3(OH)2For 9.2524g, LiOHH2O is 3.3874g, Li2CO3For 0.9282g And NaCl is 1.762g, is put it into the ball grinder of the dehydrated alcohol equipped with 17mL, adds zirconium ball, material ball ratio 1:6, With 400rpm ball milling 4h, 60 DEG C of air dry oven dry 4h are placed, 6g is weighed and is put into 480 DEG C of pre-burning 3h of resistance box, 880 DEG C of calcinings 12h, heating rate are 5 DEG C/min, obtain doped samples.Sample 3g after weighing NaCl doping again, is dissolved in equipped with distilled water It in beaker, is placed on magnetic stirring apparatus, stirs 30min, then surfactant propanesulfonate 1.74g is added into beaker, stirring After 10min, oxidant sodium thiosulfate 1.88g is then added, after stirring 10min, is cleaned, is filtered, be put into air dry oven 60 DEG C of freeze-day with constant temperature 12h, the sample of drying are placed on the filter paper in culture dish, then put one equipped with polypyrrole in culture dish In the aluminium foil capsule of 0.06g, the amount of conductive polymer material is the 2% of sample quality, is sealed with preservative film, be placed in really dry it is dry 60 DEG C of dryings for 24 hours, obtain a kind of conducting polymer coating-doping type anode material for lithium-ion batteries in case.
Embodiment 3
Ni is weighed respectively0.5Co0.2Mn0.3(OH)2For 9.2524g, LiOHH2O is 3.3874g, Li2CO3For 0.9282g And NaCl is 2.937g, is put it into the ball grinder of the dehydrated alcohol equipped with 17mL, adds zirconium ball, material ball ratio 1:6, With 400rpm ball milling 4h, 60 DEG C of air dry oven dry 4h are placed, 6g is weighed and is put into 480 DEG C of pre-burning 3h of resistance box, 880 DEG C of calcinings 12h, heating rate are 5 DEG C/min, obtain doped samples.Sample 3g after weighing NaCl doping again, is dissolved in equipped with distilled water It in beaker, is placed on magnetic stirring apparatus, stirs 30min, then surfactant propanesulfonate 1.74g is added into beaker, stirring After 10min, oxidant sodium thiosulfate 1.88g is then added, after stirring 10min, is cleaned, is filtered, be put into air dry oven 60 DEG C of freeze-day with constant temperature 12h, the sample of drying are placed on the filter paper in culture dish, then put one equipped with polypyrrole in culture dish In the aluminium foil capsule of 0.06g, the amount of conductive polymer material is the 2% of sample quality, is sealed with preservative film, be placed in really dry it is dry 60 DEG C of dryings for 24 hours, obtain a kind of doped lithium ion battery positive electrode of conducting polymer cladding in case.
Embodiment 4
Ni is weighed respectively0.5Co0.2Mn0.3(OH)2For 9.2524g, LiOHH2O is 3.3874g, Li2CO3For 0.9282g And NaCl is 0.587g, is put it into the ball grinder of the dehydrated alcohol equipped with 17mL, adds zirconium ball, material ball ratio 1:6, With 400rpm ball milling 4h, 60 DEG C of air dry oven dry 4h are placed, 6g is weighed and is put into 480 DEG C of pre-burning 3h of resistance box, 880 DEG C of calcinings 12h, heating rate are 5 DEG C/min, obtain doped samples.Sample 3g after weighing NaCl doping again, is dissolved in equipped with distilled water It in beaker, is placed on magnetic stirring apparatus, stirs 30min, then surfactant propanesulfonate 1.74g is added into beaker, stirring After 10min, oxidant sodium thiosulfate 1.88g is then added, after stirring 10min, is cleaned, is filtered, be put into air dry oven 60 DEG C of freeze-day with constant temperature 12h, the sample of drying are placed on the filter paper in culture dish, then put one equipped with polypyrrole in culture dish In the aluminium foil capsule of 0.03g, the amount of conductive polymer material is the 1% of sample quality, is sealed with preservative film, be placed in really dry it is dry 60 DEG C of dryings for 24 hours, obtain a kind of doped lithium ion battery positive electrode of conducting polymer cladding in case.
Embodiment 5
Ni is weighed respectively0.5Co0.2Mn0.3(OH)2For 9.2524g, LiOHH2O is 3.3874g, Li2CO3For 0.9282g And NaCl is 0.587g, is put it into the ball grinder of the dehydrated alcohol equipped with 17mL, adds zirconium ball, material ball ratio 1:6, With 400rpm ball milling 4h, 60 DEG C of air dry oven dry 4h are placed, 6g is weighed and is put into 480 DEG C of pre-burning 3h of resistance box, 880 DEG C of calcinings 12h, heating rate are 5 DEG C/min, obtain doped samples.Sample 3g after weighing NaCl doping again, is dissolved in equipped with distilled water It in beaker, is placed on magnetic stirring apparatus, stirs 30min, then surfactant propanesulfonate 1.74g is added into beaker, stirring After 10min, oxidant sodium thiosulfate 1.88g is then added, after stirring 10min, is cleaned, is filtered, be put into air dry oven 60 DEG C of freeze-day with constant temperature 12h, the sample of drying are placed on the filter paper in culture dish, then put one equipped with polypyrrole in culture dish In the aluminium foil capsule of 0.15g, the amount of conductive polymer material is the 5% of sample quality, is sealed with preservative film, be placed in really dry it is dry 60 DEG C of dryings for 24 hours, obtain a kind of doped lithium ion battery positive electrode of conducting polymer cladding in case.
Embodiment 6
Ni is weighed respectively0.5Co0.2Mn0.3(OH)2For 9.2524g, LiOHH2O is 3.3874g, Li2CO3For 0.9282g And KCl is 0.745g, is put it into the ball grinder of the dehydrated alcohol equipped with 17mL, adds zirconium ball, material ball ratio 1:6, With 400rpm ball milling 4h, 60 DEG C of air dry oven dry 4h are placed, 6g is weighed and is put into 480 DEG C of pre-burning 3h of resistance box, 880 DEG C of calcinings 12h, heating rate are 5 DEG C/min, obtain doped samples.
By obtained material by button cell is packed into embodiment 1, tested on blue electric tester, test voltage Range is 2.7V~4.6V, and discharge capacity is 233.7mAh g for the first time-1, capacity is 147.3mAh g after 1C is recycled 100 times-1, hold Measuring conservation rate is 82.9%, and capacity is respectively 156.2mAh g under 3C, 5C-1、146.2mAh g-1And the sample of uncoated doping Product, performance improvement are obvious.
Comparative example
Ni is weighed respectively0.5Co0.2Mn0.3(OH)2For 9.2524g, LiOHH2O is 3.3874g, Li2CO3For 0.9282g, It puts it into the ball grinder of the dehydrated alcohol equipped with 17mL, adds zirconium ball, material ball ratio 1:6 is put with 400rpm ball milling 4h It sets 60 DEG C of air dry oven dry 4h, weighs 6g and be put into 480 DEG C of resistance box pre-burning 3h, 880 DEG C of calcining 12h, heating rate 5 DEG C/min, obtain sample.
By obtained material by button cell is packed into embodiment 1, tested on blue electric tester, test voltage Range is 2.7V~4.6V, and discharge capacity is 221.1mAh g for the first time-1, capacity is 143.3mAh g after 1C is recycled 100 times-1, hold Measuring conservation rate is 78.6%, and capacity is respectively 132.5mAh g under 3C, 5C-1、100mAh g-1, coated afterwards well below first adulterating Sample.

Claims (10)

1. a kind of synthetic method of conducting polymer coating-doping type anode material for lithium-ion batteries, which is characterized in that it is described just Pole material general formula is aICP (1-a) Li1-xM1-yMexM′yO2-zTz, 0 < x≤0.05,0 < y≤0.05,0≤z≤0.05,0 < a ≤ 0.1, wherein ICP be one of polypyrrole, polyphenylene sulfide, polyaniline, polythiophene or a variety of, M Mn, Ni, Co, Al, Cr, Any one or more of Mg, Ca, Zr, Ti, Zn, Fe, Me, M ' are metallic element, and T is halogens；
The following steps are included:
A. the additive of presoma, lithium source, the element containing Me and T is added in ball grinder, the mass percentage of additive is 0.5%~10%, and a certain amount of solvent is added, ball milling is carried out with material ball ratio 1:4~1:20, rotational speed of ball-mill is 400~ 2000rpm, time are 2~16h；
B. the sample after ball milling is put into that drying box is dry, and drying temperature is 60~180 DEG C, and the time is 4~for 24 hours, after grinding uniformly 750~900 DEG C of 5~20h of heat treatment to get arrive doped lithium ion battery positive electrode sample；
C. obtained doped samples are added in distilled water, a certain proportion of surfactant, oxidant is sequentially added it Middle stirring certain time, then filter, dry, drying temperature is 60~180 DEG C, and the time is 8h~20h；
D. the sample of drying is placed in closed container, then is put into conductive polymer material in closed container, conducting polymer The quality of material is the 1%~10% of sample quality, and is in certain proportion with surfactant, the oxidant in step c, will Conductive polymer material obtains the lithium ion anode material of conducting polymer cladding in 60 DEG C~180 DEG C heated at constant temperature 2h~for 24 hours Material.
2. a kind of synthesis side of conducting polymer coating-doping type anode material for lithium-ion batteries according to claim 1 Method, it is characterised in that: Me, M ' are one of Na, K, Ba, Zn, Mg, one of T F, Cl, Br.
3. a kind of synthesis side of conducting polymer coating-doping type anode material for lithium-ion batteries according to claim 1 Method, it is characterised in that: anode active material of lithium ion battery particle surface layer is coated with conducting polymer, kernel be doping lithium from Sub- battery anode active material.
4. a kind of synthesis side of conducting polymer coating-doping type anode material for lithium-ion batteries according to claim 1 Method, it is characterised in that: in step a, the presoma is precursor of lithium ionic cell positive material, is hydroxide forerunner One kind of body, carbonate precursor, oxalate precursor, bicarbonate presoma, hydroxyl groups precursors；The lithium source is carbonic acid The combination of one or more of lithium, lithium hydroxide, lithium nitrate, lithium oxalate, lithium dihydrogen phosphate, lithium chloride.
5. a kind of synthesis side of conducting polymer coating-doping type anode material for lithium-ion batteries according to claim 1 Method, it is characterised in that: in step a, the metallic element Me is alkali metal element, alkali earth metal, the 13rd race's element, the One of 14 race's elements, transition element；The element T is selected from one of halogens.
6. a kind of synthesis side of conducting polymer coating-doping type anode material for lithium-ion batteries according to claim 5 Method, it is characterised in that: in step a, the metallic element Me is containing sodium, potassium, aluminium, magnesium, the oxide of barium, hydroxide, carbon One of hydrochlorate；The element T is selected from one of fluorine-containing, chlorine, bromine substance.
7. a kind of synthesis side of conducting polymer coating-doping type anode material for lithium-ion batteries according to claim 1 Method, it is characterised in that: in step a, the solvent is the combination of one or more of ethyl alcohol, distilled water, methanol, acetone.
8. a kind of synthesis side of conducting polymer coating-doping type anode material for lithium-ion batteries according to claim 1 Method, it is characterised in that: in step c, the surfactant is benzene sulfonic acid sodium salt, Riboflavine sodium phosphate, polyethylene glycol, stearic acid One of or a variety of combinations；The oxidant is one of sodium thiosulfate, potassium thiosulfate, ATS (Ammonium thiosulphate).
9. a kind of synthesis side of conducting polymer coating-doping type anode material for lithium-ion batteries according to claim 1 Method, it is characterised in that: in step c, the ratio of the surfactant and oxidant is 5:1~1:5；Mixing time is 10min~120min.
10. a kind of synthesis side of conducting polymer coating-doping type anode material for lithium-ion batteries according to claim 1 Method, it is characterised in that: in step d, the conductive polymer material is polypyrrole, in polyaniline, polyphenylene sulfide, polythiophene It is one or more；The mass ratio of the conductive polymer material and surfactant is 1:1~1:100, conducting polymer material The mass ratio of material and oxidant is 1:1~1:100.
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