CN105742592A - W/W2Preparation method of C/Action Carbon coated lithium ion battery anode material - Google Patents

W/W2Preparation method of C/Action Carbon coated lithium ion battery anode material Download PDF

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CN105742592A
CN105742592A CN201610119510.XA CN201610119510A CN105742592A CN 105742592 A CN105742592 A CN 105742592A CN 201610119510 A CN201610119510 A CN 201610119510A CN 105742592 A CN105742592 A CN 105742592A
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汪涛
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Gotion High Tech Co Ltd
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    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36Selection of substances as active materials, active masses, active liquids
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    • HELECTRICITY
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    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
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    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
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    • YGENERAL 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
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Abstract

The invention discloses a W/W2A preparation method of a C/Action Carbon coated lithium ion battery anode material belongs to the field of electrochemical energy storage, and comprises two steps of composite precursor preparation and reduction reaction, wherein the lithium ion battery anode material is particularly a material needing Carbon coating. The preparation method of the precursor comprises the steps of loading a tungsten source on the surface of the precursor to form a composite precursor, wherein the specific operation method comprises a sand grinding spray drying process and a wet dipping process; the reduction reaction step is that the tungsten source on the surface of the composite precursor and the carbon source are reduced into functional W/W together by a carbon-thermal hydrogen reduction method2C/Action Carbon cladding. This functional W/W2C/Action Carbon cladding layer forming process skillfully utilizes Carbon thermal reducing atmosphere in the high-temperature sintering process of the Carbon-clad lithium ion battery anode material, and then reduction is carried out by combining a short hydrogen thermal reducing process to obtain the Carbon/Action Carbon cladding layer; the defects of the coated carbon layer can be effectively repaired, and the discharge specific capacity and the rate capability of the lithium ion battery anode material can be improved. The invention has simple operation and convenient use, and can be suitable for large-scale production.

Description

A kind of W/W2The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding
Technical field
The present invention relates to a kind of W/W2The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, belongs to electrochemical energy storage field.
Background technology
Along with process of industrialization is accelerated to be skyrocketed through with economy, energy problem and environmental pollution have become as one of mankind's problem demanding prompt solution.Lithium from Sub-battery, as new generation of green rechargable power supplies, owing to having the advantages such as energy density is big, running voltage is high, good cycle, the most gradually replaces The batteries such as nickel/hydrogen, nickel/cadmium, suffer from being widely applied in fields such as electric automobile, hybrid vehicle, electric tool, 3C Product and energy storage Prospect.The anode material for lithium-ion batteries being reported in media at present is of a great variety, including cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4), lithium nickelate (LiNiO2), LiFePO4 (LiFePO4), nickel ion doped (LiNi0.5Mn1.5O4), iron manganese phosphate for lithium (LiFe1-xMnxPO4), ferric metasilicate lithium (Li2FeSiO4), Phosphoric acid vanadium lithium (Li3V2(PO4)3), lithium manganese phosphate (LiMnPO4), ternary system material (nickle cobalt lithium manganate (LiNixCoyMn1-x-yO2), nickel cobalt lithium aluminate (LiNixCoyAl1-x-yO2)), lithium-rich manganese base material (xLi2MnO3·(1-x)LiMnO2) etc.;Wherein only has mangaic acid in power lithium-ion battery field at present Lithium (LiMn2O4), LiFePO4 (LiFePO4) and ternary system material (nickle cobalt lithium manganate (LiNixCoyMn1-x-yO2), nickel cobalt lithium aluminate (LiNixCoyAl1-x-yO2)) etc. a small amount of material obtained large-scale commercial application.
LiFePO4 (LiFePO4) since Good enough and Padhi finds, high by safety, have extended cycle life, overcharging resisting and cross exoergic The advantages such as power height, good, cheap, the environmental friendliness of high temperature circulation become one of most material of current driving force field of lithium ion battery application.But The LiFePO of eigenstate4But can not directly use, main cause is eigenstate LiFePO4Electrical conductivity (10-9~10-10S/m) with lithium ion diffusion coefficient (1.8·10-14cm2/ s) the most relatively low, the transmission close to insulator, lithium ion and electronics all suffers from the biggest resistance.Identical problem equally exists In iron manganese phosphate for lithium (LiFe1-xMnxPO4), ferric metasilicate lithium (Li2FeSiO4), phosphoric acid vanadium lithium (Li3V2(PO4)3), lithium manganese phosphate (LiMnPO4) these Levy with the anode material for lithium-ion batteries that state electrical conductivity is the lowest, hinder the commercial applications process of these positive electrodes.
Numerous studies show, the lithium ion that can be substantially improved these anode material for lithium-ion batteries by metal ion mixing and material with carbon-coated surface is spread Speed and electronic conductivity.As patent CN1581537A points out that the LiFePO 4 material electronic conductivity through carbon coating layer is modified can reach 10-3S/m, its 0.2C specific discharge capacity can realize more than 145mAh/g.Yet with current LiFePO4 (LiFePO4) material heavy industrialization Produce and typically use high temperature solid-state method, the shortcoming such as existence is mutually uneven, relatively big, the broad particle distribution of crystalline size, if carbon incorporation way and Morphology Control aspect is improper, and carbon coating layer can be caused uneven, the most closely, there is carbon coating layer especially and peel off in follow-up crushing and classification processing procedure Risk, thus cause material conductivity and chemical property to be deteriorated, also can directly reduce the bulk density of LiFePO4.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of W/W2The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, Utilize the carbon thermal reduction atmosphere in anode material of carbon-coated lithium ion battery high-temperature sintering process, in conjunction with of short duration hydrogen thermal process by lithium ion cell positive The tungsten source on material precursor surface is reduced to functional W/W together with carbon source2C/Action Carbon clad, it is possible to effectively repair materials high temperature is solid The defect that the independent carbon coating layer that phase method synthesis technique prepares exists, functional W/W2The lithium ion battery of C/Action Carbon clad cladding is just Pole material high rate performance is the most excellent.
The present invention is achieved by the following technical solutions:
A kind of W/W2The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, anti-with reduction including the preparation of compound precursor thing Answering two steps, described compound precursor thing preparation process is for be supported on precursor of lithium ionic cell positive material surface by tungsten source;Described reduction reaction walks Rapid for compound precursor thing being carried out in reducing gas and noble gas high temperature sintering, make just to be coated on by controlling the technological parameter in sintering process Carbon hot hydrogen reduction reaction generating functionality W/W is passed through in the tungsten source on material precursor surface, pole2C/Action Carbon clad is coated on lithium-ion electric Pond positive electrode finished surface.
A kind of W/W of the present invention2The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, prepared by described compound precursor thing Step uses sand milling-drying process with atomizing, stoichiometrically the raw material of anode material for lithium-ion batteries is added carbon source, additive A, tungsten source, mixed Close, with water as dispersant, carry out nanorize dispersion process to slurry D by sand mill50Less than 200nm, obtain by the way of spray drying subsequently To compound precursor thing;Or
Described compound precursor thing preparation process uses wet impregnation technique, stoichiometrically the raw material of anode material for lithium-ion batteries is added carbon source, Additive B, mixing, with water as dispersant, carry out nanorize dispersion process to slurry D with sand mill50Less than 200nm, by be spray-dried Mode obtains precursor of lithium ionic cell positive material, makes tungsten source be sufficiently mixed with the carrier in presoma subsequently by the way of solution impregnation is evaporated To compound precursor thing.
A kind of W/W of the present invention2The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, described reduction reaction step is adopted Use temperature programming sintering process:
(1)H2Atmosphere is warming up to 250~350 DEG C, is incubated 20~40min, then raises temperature to 550~650 DEG C, be incubated 20~40min;
(2)H2Atmosphere is warming up to the sintering temperature of positive electrode, is incubated 50~70min;
(3) by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until material has sintered the required time;
(4) noble gas N2Or Ar sintering atmosphere is cooled to 450~550 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace.
Anode material for lithium-ion batteries of the present invention refers in particular to LiFePO4 (LiFePO4), iron manganese phosphate for lithium (LiFe1-xMnxPO4), phosphoric acid vanadium lithium (Li3V2(PO4)3), lithium manganese phosphate (LiMnPO4), ferric metasilicate lithium (Li2FeSiO4) arbitrary in this kind of anode material for lithium-ion batteries needing carbon to be coated with Kind.
Tungsten source of the present invention is selected from ammonium paratungstate and/or ammonium metatungstate, and its content is 0.5~3% (wt) of compound precursor thing.
Additive A of the present invention is selected from oxalic acid and/or citric acid, and described additive A is 1:2~2:1 with the mass ratio in tungsten source.
The additive B of the present invention one or more mixture in Super P, Vulcan Carbon, petroleum coke;Described interpolation Agent B and tungsten source quality ratio are 2:1~8:1.
Carbon source of the present invention is selected from sucrose, glucose, maltose, starch, cyclodextrin, phenolic resin, epoxy resin, Polyethylene Glycol, Colophonium One or more mixture in this kind of organic carbon source.
Reduction reaction stage heating rate of the present invention is 1~3 DEG C/min;Temperature-fall period speed is 1~3 DEG C/min.
The beneficial effects of the present invention is:
First the present invention is soaked by sand milling-drying process with atomizing or wet method at the precursor of lithium ionic cell positive material preparatory phase needing carbon to be coated with Tungsten source is supported on presoma surface by stain technique, and the reducing atmosphere formed followed by carbon source pyrolysis in high-temperature sintering process, in conjunction with the of short duration hot mistake of hydrogen Tungsten source can be reduced to functional W/W together with carbon source by Cheng Caiyong temperature programming sintering process2C/Action Carbon clad is coated on lithium ion Cell positive material finished surface, it is possible to effectively repair and form defect present in independent carbon coating layer.Due to W/W2C is the good material of electric conductivity Material, it is thus possible to be effectively improved the chemical property of anode material for lithium-ion batteries.The present invention is unique in that compound precursor thing preparatory phase tungsten The mode of loading in source: for sand milling-drying process with atomizing, be additive by adding oxalic acid or citric acid, tungsten source ammonium paratungstate or metatungstic acid can be promoted Ammonium evaporates film forming at precursor of lithium ionic cell positive material surface crystallization;A certain amount of specific surface can be added in predecessor for wet impregnation technique Long-pending bigger activated carbon is as tungsten source ammonium paratungstate or the POL of ammonium metatungstate, and then beneficially later stage tungsten source load is firm;Load the most complete Tungsten source become realize in product generate the most functional W/W of performance2The key of C/Action Carbon clad.Present invention process is simple, behaviour Facilitate, large-scale production can be suitable for.
Accompanying drawing explanation
W/W in Fig. 1: embodiment 52LiFePO4 (the LiFePO of C/Action Carbon clad cladding4) material different multiplying charging and discharging curve;
LiFePO4 (the LiFePO of common carbon coating layer cladding in Fig. 2: comparative example 14) material different multiplying charging and discharging curve;
W/W in Fig. 3: embodiment 62Lithium ferric manganese phosphate (the LiFe of C/Action Carbon clad cladding0.3Mn0.7PO4) material different multiplying charge and discharge Electricity curve;
Lithium ferric manganese phosphate (the LiFe of common carbon coating layer cladding in Fig. 4: comparative example 20.3Mn0.7PO4) material different multiplying charging and discharging curve.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1:
Compound precursor thing preparatory phase:
With lithium manganese phosphate (LiMnPO4) add the lithium source of stoichiometric proportion based on molecular formula, phosphorus source, manganese source are raw material, add the poly-second of carbon source two Alcohol, the tungsten source ammonium paratungstate of gross mass 0.5% and the additive oxalic acid with the 2 times of quality in tungsten source, carry out nanorize for dispersant by sand mill with water Dispersion process is until slurry granularity D50Less than 200nm;Carry out granulating and drying by spray dried form subsequently and obtain compound precursor thing.
The reduction reaction stage:
A, by compound precursor thing at H2Atmosphere is warming up to 250 DEG C, is incubated 40min, then raises temperature to 600 DEG C, be incubated 20min;
b、H2Atmosphere is warming up to LiMnPO4The sintering temperature of material, is incubated 60min;
C, by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until LiMnPO4Material has sintered;
D, with noble gas N2Or Ar sintering atmosphere is cooled to 450 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace and i.e. can get functional W/W2Lithium manganese phosphate (the LiMnPO of C/Action Carbon clad cladding4) positive electrode;
Wherein temperature rise period speed is 1 DEG C/min;Temperature-fall period speed is 3 DEG C/min.
Embodiment 2:
Compound precursor thing preparatory phase:
With ferric metasilicate lithium (Li2FeSiO4) add the lithium source of stoichiometric proportion based on molecular formula, source of iron, silicon source are raw material, add carbon source epoxy resin With additive Super P, carry out nanorize dispersion process with water for dispersant by sand mill until slurry granularity D50Less than 200nm, with spray dried Dry mode carries out granulating and drying and obtains presoma;Subsequently with ammonium metatungstate for tungsten source, impregnation method makes ammonium metatungstate enter on presoma surface in a wet process Row load obtains compound precursor thing, is 1% (wt) by controlling tungsten source ammonium metatungstate content in the state modulator compound precursor things such as dip time and temperature. Wherein additive Super P mass is 8 times of tungsten source ammonium metatungstate.
The reduction reaction stage:
A, by compound precursor thing at H2Atmosphere is warming up to 350 DEG C, is incubated 30min, then raises temperature to 600 DEG C, be incubated 40min;
b、H2Atmosphere is warming up to Li2SiPO4The sintering temperature of material, is incubated 60min;
C, by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until Li2SiPO4Material has sintered;
D, with noble gas N2Or Ar sintering atmosphere is cooled to 550 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace and i.e. can get functional W/W2Ferric metasilicate lithium (the Li of C/Action Carbon clad cladding2FeSiO4) positive electrode;
Wherein temperature rise period speed is 2 DEG C/min;Temperature-fall period speed is 2 DEG C/min.
Embodiment 3:
Compound precursor thing preparatory phase:
With phosphoric acid vanadium lithium (Li3V2(PO4)3) add the lithium source of stoichiometric proportion based on molecular formula, phosphorus source, vanadium source are raw material, add carbon source Colophonium, The tungsten source ammonium metatungstate of gross mass 1.5% and the additive citric acid with tungsten source 50% mass, carry out nanorize for dispersant by sand mill with water and divide Dissipate and process until slurry granularity D50Less than 200nm;Carry out granulating and drying by spray dried form subsequently and obtain compound precursor thing.
The reduction reaction stage:
A, by compound precursor thing at H2Atmosphere is warming up to 300 DEG C, is incubated 20min, then raises temperature to 550 DEG C, be incubated 30min;
b、H2Atmosphere is warming up to Li3V2(PO4)3The sintering temperature of material, is incubated 70min;
C, by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until Li3V2(PO4)3Material has sintered;
D, with noble gas N2Or Ar sintering atmosphere is cooled to 500 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace and i.e. can get functional W/W2Phosphoric acid vanadium lithium (the Li of C/Action Carbon clad cladding3V2(PO4)3) positive electrode;
Wherein temperature rise period speed is 1 DEG C/min;Temperature-fall period speed is 2 DEG C/min.
Embodiment 4:
Compound precursor thing preparatory phase:
With LiFePO4 (LiFePO4) add the lithium source of stoichiometric proportion based on molecular formula, source of iron, phosphorus source are raw material, add carbon source sucrose and interpolation Agent petroleum coke, carries out nanorize dispersion process with water for dispersant by sand mill until slurry granularity D50Less than 200nm, with spray dried form Carry out granulating and drying and obtain presoma;Subsequently with ammonium paratungstate for tungsten source, impregnation method makes ammonium metatungstate load on presoma surface in a wet process Obtain compound precursor thing, be 2% (wt) by controlling tungsten source ammonium metatungstate content in the state modulator compound precursor things such as dip time and temperature.Wherein add Add that agent Petroleum Coke is tungsten source ammonium metatungstate 2 times.
The reduction reaction stage:
A, by compound precursor thing at H2Atmosphere is warming up to 300 DEG C, is incubated 30min, then raises temperature to 650 DEG C, be incubated 30min;
b、H2Atmosphere is warming up to LiFePO4The sintering temperature of material, is incubated 50min;
C, by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until LiFePO4Material has sintered;
D, with noble gas N2Or Ar sintering atmosphere is cooled to 500 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace and i.e. can get functional W/W2LiFePO4 (the LiFePO of C/Action Carbon clad cladding4) positive electrode;
Wherein temperature rise period speed is 3 DEG C/min;Temperature-fall period speed is 1 DEG C/min.
Embodiment 5:
Compound precursor thing preparatory phase:
With LiFePO4 (LiFePO4) add the lithium source of stoichiometric proportion based on molecular formula, phosphorus source, source of iron are raw material, add carbon source glucose, The tungsten source ammonium paratungstate of gross mass 2% and the additive oxalic acid with quality such as tungsten sources, carried out at nanorize dispersion by sand mill with water for dispersant Reason is until slurry granularity D50Less than 200nm;Carry out granulating and drying by spray dried form subsequently and obtain compound precursor thing.
The reduction reaction stage:
A, by compound precursor thing at H2Atmosphere is warming up to 300 DEG C, is incubated 30min, then raises temperature to 600 DEG C, be incubated 30min;
b、H2Atmosphere is warming up to LiFePO4The sintering temperature of material, is incubated 60min;
C, by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until LiFePO4Material has sintered;
D, with noble gas N2Or Ar sintering atmosphere is cooled to 500 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace and i.e. can get functional W/W2LiFePO4 (the LiFePO of C/Action Carbon clad cladding4) positive electrode;
Wherein temperature rise period speed is 2 DEG C/min;Temperature-fall period speed is 2 DEG C/min.
Comparative example 1:
Predecessor preparatory phase:
With LiFePO4 (LiFePO4) add the lithium source of stoichiometric proportion based on molecular formula, phosphorus source, source of iron are raw material, add carbon source glucose, The oxalic acid of gross mass 2%, carries out nanorize dispersion process with water for dispersant by sand mill until slurry granularity D50Less than 200nm;Lead to subsequently Cross spray dried form to carry out granulating and drying and obtain predecessor.
The high temperature sintering stage:
A, by predecessor at noble gas N2Or Ar atmosphere is warming up to 300 DEG C, it is incubated 30min, then raises temperature to 600 DEG C, be incubated 30min;
B, noble gas N2Or Ar atmosphere is warming up to LiFePO4The sintering temperature of material, insulation is until LiFePO4Material has sintered, with stove It is cooled to room temperature and i.e. can get the LiFePO4 (LiFePO of common carbon coating layer cladding4) positive electrode;
Wherein temperature rise period speed is 2 DEG C/min;Temperature-fall period speed is 2 DEG C/min.
Embodiment 6:
Compound precursor thing preparatory phase:
With lithium ferric manganese phosphate (LiFe0.3Mn0.7PO4) add the lithium source of stoichiometric proportion based on molecular formula, source of iron, phosphorus source, manganese source are raw material, add Carbon source sucrose and additive Vulcan Carbon, carry out nanorize dispersion process with water for dispersant by sand mill until slurry granularity D50It is less than 200nm, carries out granulating and drying with spray dried form and obtains presoma;Subsequently with ammonium metatungstate for tungsten source, impregnation method makes metatungstic acid in a wet process Ammonium carries out load on presoma surface and obtains compound precursor thing, by controlling tungsten source metatungstic acid in the state modulator compound precursor things such as dip time and temperature Ammonium content is 3% (wt).Wherein additive Vulcan Carbon mass is 4 times of tungsten source ammonium metatungstate.
The reduction reaction stage:
A, by compound precursor thing at H2Atmosphere is warming up to 300 DEG C, is incubated 30min, then raises temperature to 600 DEG C, be incubated 30min;
b、H2Atmosphere is warming up to LiFe0.3Mn0.7PO4The sintering temperature of material, is incubated 60min;
C, by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until LiFe0.3Mn0.7PO4Material has sintered;
D, with noble gas N2Or Ar sintering atmosphere is cooled to 500 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace and i.e. can get functional W/W2Lithium ferric manganese phosphate (the LiFe0.3Mn0.7PO of C/Action Carbon clad cladding4) positive electrode;
Wherein temperature rise period speed is 2 DEG C/min;Temperature-fall period speed is 2 DEG C/min.
Comparative example 2:
Predecessor preparatory phase:
With lithium ferric manganese phosphate (LiFe0.3Mn0.7PO4) add the lithium source of stoichiometric proportion based on molecular formula, source of iron, phosphorus source, manganese source are raw material, add The Vulcan Carbon of carbon source sucrose and gross mass 12%, carries out nanorize dispersion process with water for dispersant by sand mill until slurry granularity D50 Less than 200nm, carry out granulating and drying with spray dried form and obtain presoma.
The high temperature sintering stage:
A, by predecessor at noble gas N2Or Ar atmosphere is warming up to 300 DEG C, it is incubated 30min, then raises temperature to 600 DEG C, be incubated 30min;
B, noble gas N2Or Ar atmosphere is warming up to LiFe0.3Mn0.7PO4The sintering temperature of material, insulation is until LiFe0.3Mn0.7PO4Material Sintering completes, and cools to room temperature with the furnace and i.e. can get the lithium ferric manganese phosphate (LiFe of common carbon coating layer cladding0.3Mn0.7PO4) positive electrode;
Wherein temperature rise period speed is 2 DEG C/min;Temperature-fall period speed is 2 DEG C/min.
The functional W/W prepared for the detection present invention2The chemical property of the anode material for lithium-ion batteries of C/Action Carbon clad cladding, Use 2016 button cells that it is carried out electrochemistry evaluation and test.The W/W obtained with embodiment 5 and comparative example 12C/Action Carbon clad with LiFePO4 (the LiFePO of common carbon coating layer cladding4) material, and the W/W that embodiment 6 obtains with comparative example 22C/Action Carbon bag Lithium ferric manganese phosphate (the LiFe that coating is coated with common carbon coating layer0.3Mn0.7PO4) material is as positive pole, with positive active material: conductive agent Super P: The mass ratio of bonding agent Kynoar (PVDF)=80:10:10 carries out closing slurry, is subsequently coated at the baking of 120 DEG C of utter misery aluminum foil current collector surface 2h obtains anode pole piece, is assembled into button cell in full Ar glove box, and wherein metal lithium sheet is to electrode, and clegard2400 is barrier film, The LiPF of 1mol/L6/ EC+DEC+DMC solution is electrolyte, uses Land battery test system to carry out constant current charge-discharge test, result such as figure 1~4, table 1~2.
LiFePO in table 1 embodiment 5 and comparative example 14Specific discharge capacity
Discharge-rate 0.2C 0.5C 1C 2C
Embodiment 5 (mAh.g-1) 154.5 144.7 140.2 129.3
Comparative example 1 (mAh.g-1) 152.7 141.7 136.5 125.0
LiFe in table 2 embodiment 6 and comparative example 20.3Mn0.7PO4Specific discharge capacity
Discharge-rate 0.2C 0.5C 1C 2C 3C
Embodiment 6 (mAh.g-1) 131.6 127.8 125.6 121.8 118.5
Comparative example 2 (mAh.g-1) 129.4 121.9 117.3 115.7 114.8
Fig. 1 Yu Fig. 2 provides two kinds of LiFePO4 (LiFePO4) charging and discharging curve under material different multiplying, the electric discharge ratio under different multiplying listed by table 1 Capacity, comprehensive analysis finds W/W2The LiFePO of C/Action Carbon cladding4(154.5mAh.g-1) more common carbon cladding LiFePO4(152.7 mAh.g-1) material 0.2C specific discharge capacity 2mAh.g to be exceeded-1, the LiFePO of carbon the most common for the specific discharge capacity under bigger multiplying power cladding4 Want height, embody through W/W2Good LiFePO after C/Action Carbon cladding4There is discharge performance and the high rate performance of excellence.
Fig. 3 Yu Fig. 4 give also two kinds of lithium ferric manganese phosphate (LiFe simultaneously0.3Mn0.7PO4) charging and discharging curve of material different multiplying, under different multiplying Specific discharge capacity is listed in table 2.Result display W/W2The LiFe of C/Action Carbon cladding0.3Mn0.7PO4Material discharging performance is with high rate performance all More common carbon cladding LiFe0.3Mn0.7PO4Material to be got well, and further demonstrate that functional W/W2C/Action Carbon cladding can effectively modified lithium The chemical property of ion battery positive electrode.
Above content is to combine concrete preferred implementation further description made for the present invention, it is impossible to assert being embodied as only of the present invention It is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, it is also possible to Make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.

Claims (9)

1. a W/W2The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterized in that: including the preparation of compound precursor thing and two steps of reduction reaction, described compound precursor thing preparation process is for be supported on precursor of lithium ionic cell positive material surface by tungsten source;Described reduction reaction step, for compound precursor thing carries out in reducing gas and noble gas high temperature sintering, makes to be coated on the tungsten source on positive electrode material precursor surface by carbon hot hydrogen reduction reaction generating functionality W/W by controlling the technological parameter in sintering process2C/Action Carbon clad is coated on anode material for lithium-ion batteries finished surface.
A kind of W/W the most according to claim 12The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterized in that: described compound precursor thing preparation process uses sand milling-drying process with atomizing, stoichiometrically the raw material of anode material for lithium-ion batteries is added carbon source, additive A, tungsten source, mixing, with water as dispersant, carry out nanorize dispersion process to slurry D by sand mill50Less than 200nm, by the way of spray drying, obtain compound precursor thing subsequently;Or
Described compound precursor thing preparation process uses wet impregnation technique, and the raw material of anode material for lithium-ion batteries stoichiometrically adds carbon source, additive B, mixing, with water as dispersant, carries out nanorize dispersion process to slurry D with sand mill50Less than 200nm, by the way of spray drying, obtain precursor of lithium ionic cell positive material, make tungsten source be sufficiently mixed with the carrier in presoma subsequently by the way of solution impregnation is evaporated and obtain compound precursor thing.
A kind of W/W the most according to claim 1 and 22C/Action The method for preparing anode material of lithium-ion battery of Carbon cladding, it is characterised in that described reduction reaction step employing temperature programming sintering process:
(1) H2Atmosphere is warming up to 250 ~ 350 DEG C, is incubated 20 ~ 40min, then raises temperature to 550 ~ 650 DEG C, be incubated 20 ~ 40min;
(2) H2Atmosphere is warming up to the sintering temperature of positive electrode, is incubated 50 ~ 70min;
(3) by sintering atmosphere from H2Switch to noble gas N2Or Ar, insulation is until material has sintered the required time;
(4) noble gas N2Or Ar sintering atmosphere is cooled to 450 ~ 550 DEG C, switch to H subsequently2Atmosphere cools to room temperature with the furnace.
A kind of W/W the most according to claim 12The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterised in that: described anode material for lithium-ion batteries is LiFePO4, iron manganese phosphate for lithium, phosphoric acid vanadium lithium, lithium manganese phosphate, any one in ferric metasilicate lithium.
A kind of W/W the most according to claim 1 and 22C/Action The method for preparing anode material of lithium-ion battery of Carbon cladding, it is characterised in that: described tungsten source is selected from ammonium paratungstate and/or ammonium metatungstate, and its content is 0.5 ~ 3%wt of compound precursor thing.
A kind of W/W the most according to claim 22The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterised in that: described additive A is selected from oxalic acid and/or citric acid, and described additive A is 1:2 ~ 2:1 with the mass ratio in tungsten source.
A kind of W/W the most according to claim 22The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterised in that: described additive B is selected from Super P, Vulcan One or more mixture in Carbon, petroleum coke;Described additive B and tungsten source quality ratio are 2:1 ~ 8:1.
A kind of W/W the most according to claim 22The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterised in that: the described carbon source one or more mixture in sucrose, glucose, maltose, starch, cyclodextrin, phenolic resin, epoxy resin, Polyethylene Glycol, Colophonium.
A kind of W/W the most according to claim 32The method for preparing anode material of lithium-ion battery of C/Action Carbon cladding, it is characterised in that: described reduction reaction step temperature-rise period speed is 1 ~ 3 DEG C/min;Temperature-fall period speed is 1 ~ 3 DEG C/min.
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CN107978743A (en) * 2017-11-20 2018-05-01 中南大学 A kind of sodium-ion battery positive material and preparation method thereof, sodium-ion battery
CN110299515A (en) * 2018-03-23 2019-10-01 比亚迪股份有限公司 A kind of positive electrode active materials and preparation method thereof, Anode and battery
CN110517808A (en) * 2019-08-05 2019-11-29 中国民用航空飞行学院 A kind of composite conductive thin film and preparation method thereof based on silver nanowires
CN115974035A (en) * 2022-12-28 2023-04-18 唐山亨坤新能源材料有限公司 Method for adjusting lithium iron phosphate carbon-bundle

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CN103618065A (en) * 2013-11-20 2014-03-05 浙江南都电源动力股份有限公司 Lithium iron phosphate material and preparation method thereof
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CN106935840A (en) * 2017-05-23 2017-07-07 苏州思创源博电子科技有限公司 A kind of preparation method of tungsten coated LiFePO 4 for lithium ion batteries positive electrode
CN107978743A (en) * 2017-11-20 2018-05-01 中南大学 A kind of sodium-ion battery positive material and preparation method thereof, sodium-ion battery
CN110299515A (en) * 2018-03-23 2019-10-01 比亚迪股份有限公司 A kind of positive electrode active materials and preparation method thereof, Anode and battery
CN110299515B (en) * 2018-03-23 2023-08-08 比亚迪股份有限公司 Positive electrode active material, preparation method thereof, positive electrode and battery
CN110517808A (en) * 2019-08-05 2019-11-29 中国民用航空飞行学院 A kind of composite conductive thin film and preparation method thereof based on silver nanowires
CN110517808B (en) * 2019-08-05 2021-06-18 中国民用航空飞行学院 Composite conductive film based on silver nanowires and preparation method thereof
CN115974035A (en) * 2022-12-28 2023-04-18 唐山亨坤新能源材料有限公司 Method for adjusting lithium iron phosphate carbon-bundle

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