CN103985876B - Method for performing in-situ controllable coating on lithium ion battery electrode material by phenolic resin - Google Patents
Method for performing in-situ controllable coating on lithium ion battery electrode material by phenolic resin Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The invention discloses a method for performing in-situ controllable coating on a lithium ion battery electrode material by a phenolic resin. The method comprises the following steps: (1) putting a lithium ion battery electrode material or a precursor for synthesizing the lithium ion battery electrode material into a mixed solution of water and ethanol, sequentially adding phenol, ammonia water and aldehyde for stirring at a certain temperature, and drying an obtained precipitate, thereby obtaining an intermediate product; and (2) calcining the intermediate product obtained in the step (1) in an inert atmosphere or a reducing atmosphere, and cooling to room temperature, thereby finishing coating of a carbon layer, or mixing the intermediate product obtained from the precursor in the step (1) with a compound containing lithium ions, grinding, calcining, and cooling to room temperature, thereby finishing coating of the carbon layer. The method is simple and feasible, the thickness of the coated carbon layer can be systematically regulated and optimized, the electronic conductivity and ionic conductivity of a polyanionic positive electrode material are obviously improved, and the cycle performance and rate performance of the material are optimized.
Description
Technical field
The invention belongs to field of lithium ion battery material is and in particular to a kind of utilize phenolic resin to lithium ion cell electrode
The method that material carries out controlled cladding in situ.
Background technology
Polyanion positive electrode LixMXO4(M represents transition metal, and X represents phosphorus, silicon or sulphur, and x is positive number) is lithium
Important one kind in ion battery material, has environmental friendliness, with low cost, security is good, specific capacity is high, good cycling stability
The advantages of, it is particularly suitable for the electrokinetic cell application of the aspects such as electric motor car, energy-storage battery.However, due to this kind of material itself
Architectural characteristic, lithium ion can only transmit along (010) one-dimensional square, therefore electronic conductivity and ionic conductivity low so that
During de- lithium and embedding lithium, electronics can not timely import and derive, and lead to the utilization rate of active material low, and capacity portions damage
Lose it is difficult to meet the requirement of electrokinetic cell high rate charge-discharge.Can significantly improve in material surface cladding easy conductive material and lead
Electrically or synthesis to have the product of nano-sized particles to shorten lithium ion diffusion path be that to solve this village material electronic conductivity low
The main method low with ionic conductivity, thus improve its high rate performance.
On the other hand, for some negative materials widely studied at present, such as Si, SnO2Coat except permissible Deng, carbon-coating
Improve beyond electrical conductivity, can also to a certain degree suppress such material in Li+The huge body producing during embedding and deviating from
Long-pending expansion, it is to avoid electrode material and the directly contact of electrolyte, has weight to capacity, cycle performance and the security improving material
The meaning wanted.
Carbon coating method widely used at present predominantly adds a kind of organic matter containing C, such as glucose, sucrose, lemon
Acid, ethylene glycol etc., carbon coating is carried out by pyrocarbon thermal decomposition.However, it is not bery homogeneous to thermally decompose coated carbon-coating by carbon
With continuous, there is a lot of carbon-rich zone domain (thick carbon-coating) and carbon-poor area domain (thin carbon layer) so that material granule all directions electricity
Sub- transmittability is unbalanced, and therefore the electrical conductivity in all directions also differs, and easily produces polarization phenomena.Additionally, by being somebody's turn to do
The reaction condition that the method for kind carries out bag carbon is harsher, generally requires and enters under conditions of high-energy ball milling or high temperature hydro-thermal reaction
OK, complex operation, and reaction temperature is higher, is unfavorable for large-scale application.For lifting the performance of battery it is necessary to electrode material
The covered effect on surface is accurately effectively regulated and controled, and the rational synthetic method of exploiting economy, realizes electrode material performance
Optimize.
A kind of vapour deposition process has been invented with to LiFePO in Chinese patent 200710011883.64Carry out controlled carbon-coating bag
Cover.Adopt acetylene or propylene in invention as carbon-source gas, by change chemical vapor deposition processes parameter (depositing temperature,
Sedimentation time, carbon source gas volumetric percentage) coated carbon layers having thicknesses are controlled in 2-50nm.The method is to equipment requirement
Height, needs individually purchase acetylene or propylene gas and related air distributing device, and production cost is higher, is unfavorable for that industrial-scale should
With.A kind of controlled cladding FePO has been invented in Chinese patent 201010604083.74Method, using hydroxybenzoic acid as having
Machine carbon source, realizes controlled cladding by changing the consumption of hydroxybenzoic acid.But in this method, coating reaction needs in height
Carry out under conditions of temperature heating, and the TEM figure appended by from patent finds out, covered effect is not still highly desirable, carbon-coating is not bery homogeneous
Continuously.
Content of the invention
It is an object of the invention to provide a kind of method that using phenolic resin, electrode material is carried out with controlled cladding in situ.
The phenolic resin polymerisation that the present invention provides refers to phenol and aldehyde and generates phenolic resin through condensation polymerization process
Reaction, using this polymerisation lithium ion battery electrode material surface in situ carry out the controlled method for coating of carbon-coating be a
Or b；
Wherein, the method carrying out carbon-coating cladding to the surface of lithium ion battery electrode material, is method a or b；
Wherein, method a comprises the steps：
1) raw material is placed in the mixed liquor being made up of water and ethanol, sequentially adds phenolic compound, ammoniacal liquor and aldehydes
The aqueous solution stirring of compound, collects precipitation, obtains intermediate product；
Wherein, described raw material is anode material for lithium-ion batteries or negative material；
When described raw material is positive electrode, gained intermediate product is designated as intermediate product a；
When described raw material is presoma I, gained intermediate product is designated as intermediate product b；
When described raw material is presoma II, gained intermediate product is designated as intermediate product c；
When described raw material is presoma III, gained intermediate product is designated as intermediate product d；
When described raw material is negative material, gained intermediate product is designated as intermediate product e；
When described raw material is presoma IV, gained intermediate product is designated as intermediate product f；
2) by step 1) gained intermediate product a calcined, naturally cools to room temperature, complete the cladding of described carbon-coating；Or
Person,
By step 1) gained intermediate product b mixed with the compound containing lithium ion and calcined, and naturally cools to room temperature,
Complete the cladding of described carbon-coating；Or,
By step 1) gained intermediate product c mixed with the compound containing lithium ion and the ammonium salt containing phosphate radical and forged
Burn, naturally cool to room temperature, complete the cladding of described carbon-coating；Or,
By step 1) gained intermediate product d, the compound containing lithium ion and iron containing compoundses mixing calcined, natural
It is cooled to room temperature, complete the cladding of described carbon-coating；
By step 1) gained intermediate product e calcined, naturally cools to room temperature, complete the cladding of described carbon-coating；Or,
By step 1) gained intermediate product f mixed with the compound containing lithium ion and calcined, and naturally cools to room temperature,
Complete the cladding of described carbon-coating；
Method b comprises the steps：
3) raw material is placed in the mixed liquor being made up of water and ethanol, sequentially adds phenolic compound, ammoniacal liquor and aldehydes
The aqueous solution stirring of compound, collects precipitation, obtains intermediate product；
Wherein, described raw material is anode material for lithium-ion batteries or negative material；
When described raw material is positive electrode, gained intermediate product is designated as intermediate product a；
When described raw material is presoma I, gained intermediate product is designated as intermediate product b；
When described raw material is presoma II, gained intermediate product is designated as intermediate product c；
When described raw material is presoma III, gained intermediate product is designated as intermediate product d；
When described raw material is negative material, gained intermediate product is designated as intermediate product e；
When described raw material is presoma IV, gained intermediate product is designated as intermediate product f；
4) by step 3) gained intermediate product is placed in the mixed liquor being made up of water and ethanol, sequentially adds phenols chemical combination
The aqueous solution stirring of thing, ammoniacal liquor and aldehyde compound, collects precipitation, obtains secondary intermediate product；
Wherein, when described intermediate product is intermediate product a, the secondary intermediate product of gained is designated as secondary intermediate product I；
When described intermediate product is intermediate product b, the secondary intermediate product of gained is designated as secondary intermediate product II；
When described intermediate product is intermediate product c, the secondary intermediate product of gained is designated as secondary intermediate product III；
When described intermediate product is intermediate product d, the secondary intermediate product of gained is designated as secondary intermediate product IV；
When described intermediate product is intermediate product e, the secondary intermediate product of gained is designated as secondary intermediate product V；
When described intermediate product is intermediate product f, the secondary intermediate product of gained is designated as secondary intermediate product VI；
5) by step 4) gained secondary intermediate product I calcined, and naturally cools to room temperature, completes described carbon-coating cladding；
Or,
By step 4) gained secondary intermediate product II mixed with the compound containing lithium ion and calcined, naturally cool to
Room temperature, completes described carbon-coating cladding；Or,
By step 4) gained secondary intermediate product III, the compound containing lithium ion and the ammonium salt containing phosphate radical mixing
Calcined, naturally cooled to room temperature, completed described carbon-coating cladding；Or,
By step 4) gained secondary intermediate product IV, the compound containing lithium ion and iron containing compoundses mixing forged
Burn, naturally cool to room temperature, complete described carbon-coating cladding.
By step 4) gained secondary intermediate product V calcined, and naturally cools to room temperature, completes described carbon-coating cladding；Or
Person,
By step 4) gained secondary intermediate product VI mixed with the compound containing lithium ion and calcined, naturally cool to
Room temperature, completes described carbon-coating cladding.
The described step 1 of said method) in, the formula of positive electrode is LixMXO4；
Wherein, M is transition metal, is chosen in particular from least one in Fe, Mn, V, Co and Ni；
X is phosphorus, silicon or sulphur；
0<x<2, concretely 0<x<1；
Described positive electrode is chosen in particular from LiFePO4、LiMnPO4、LiMn1-xFexPO4、Li3V2(PO4)3、Li2FeSiO4、
LiCoPO4And LiNiPO4In at least one；LiMn1-xFexPO4It is specially LiMn5Fe5PO4；
Described negative material is selected from Si, SnO2、TiO2And Li4Ti5O12In at least one；
The grain graininess of described positive electrode and negative material is 50nm-1 μm；
Described presoma I is FePO4、Fe3(PO4)2,MnPO4、Mn3(PO4)2Or Mn1-xFexPO4；Described Mn1-xFexPO4
In, 0<x<1；
Described presoma II is Fe2P2O7、Mn2P2O7Or (Mn1-xFex)2P2O7；Described Mn1-xFexPO4In, 0<x<1；
Described presoma III is Si or SiO2；
Described presoma IV is TiO2；
The grain graininess of described presoma I, II, III and IV is 10-500nm；
Described step 1), 3) and 4) in, described phenolic compound is in the phenol containing substituent and phenol derivatives
At least one；Wherein, described substituent is selected from the alkyl of C1-C5, amino, the aminoalkyl of C1-C5, hydroxyl, sulfydryl, nitro, sulphur
At least one in acidic group, the alkoxyl of the carboxyl of C1-C5, halogen and C1-C5；
The described phenol containing substituent is chosen in particular from methylphenol, benzenediol, benzenetriol, amino-phenol and nitrophenol
In at least one；
Wherein, described methylphenol is specially ortho-methyl phenol, m-methyl phenol or p-methyl phenol；Described benzenediol tool
Body is catechol, resorcinol or hydroquinones；Described benzenetriol be specially pyrogaelol, oxyhydroquinone or
Benzenetriol；Described amino-phenol is specially o-aminophenol, m-aminophenol or para-aminophenol；Described nitrophenol is specially
The nitrophenol that ortho position, meta, contraposition replace；
Described phenol derivatives is specially naphthols；
Described aldehyde compound is selected from least one in formaldehyde, acetaldehyde, propionic aldehyde and glutaraldehyde；
The mass percentage concentration of the aqueous solution of described aldehyde compound is 10-40%, specially 30-40%, more specifically
37%；
Described step 1), 3) and 4) in, in the described mixed liquor being made up of water and ethanol, the volume ratio of water and ethanol is
0.5-50：1, specially 2：1、2.1:1、2.5:1；
The mass percentage concentration of described ammoniacal liquor is 25-28%, specially 25%；
Described step 1) and 3) in, the mole dosage of raw material, phenolic compound, aldehyde compound and ammoniacal liquor is than for 0.1-
60：0.05-30：0.05-30：0.5-15, specially 14：1：3：3、7：1：3：3、57：0.65：13.4：13、25.4：0.7：
13.4：13、31.7：9.09：13.4：13、19：9.09：13.4：13、19：18：13.4：13、32：9：13.4：13、19：27：
13.4：13、10：18：13.4：13、17:18：13.4：13、12:9：13.4：13；
Described step 4) in, the mole dosage ratio of secondary intermediate product, phenolic compound, aldehyde compound and ammoniacal liquor is
0.1-60：0.05-30：0.05-30：0.5-15.
Described step 1), 3) and 4) in whipping step, temperature is 20-200 DEG C, specially room temperature, and the time is 0.3-48
Hour, specially 12 hours.
Described step 2) and 5) in, the described compound containing lithium ion is lithium hydroxide, lithium acetate, lithium carbonate, nitric acid
Lithium, lithium sulfate, lithium dihydrogen phosphate, lithium oxalate, lithium formate, lithium metasilicate, lithium laurate, lithium citrate or malic acid lithium；
The described ammonium salt containing phosphate radical is diammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate；
Described iron containing compoundses are ferrous oxalate, iron chloride, ferric nitrate, ferrous sulfate, acetylacetone,2,4-pentanedione are ferrous or levulinic
Ketone iron.
Described step 2) in, intermediate product b with the mole dosage ratio that feeds intake of Li element in the compound containing lithium ion is
1：1.0-1.2；
The throwing of P element in Li element and the ammonium salt containing phosphate radical in described intermediate product c, the compound containing lithium ion
Material mole dosage ratio is for 1：1.0-1.2：1；
In Li element and iron containing compoundses in described intermediate product d, the compound containing lithium ion, feeding intake of Fe element is rubbed
Your amount ratio is 1：2.0-2.4：1；
In described intermediate product f, the compound containing lithium ion, the mole dosage that feeds intake of Li element is than for 5：4-4.12；
Described step 5) in, the mole dosage that feeds intake of Li element in secondary intermediate product II and the compound containing lithium ion
Than for 1：1.0-1.1；
P element in Li element and the ammonium salt containing phosphate radical in secondary intermediate product III, the compound containing lithium ion
The mole dosage that feeds intake is than for 1：1.0-1.2：1；
In Li element and iron containing compoundses in secondary intermediate product IV, the compound containing lithium ion, feeding intake of Fe element is rubbed
Your amount ratio is 1：2.0-2.4：1；
The mole dosage that feeds intake of secondary intermediate product VI and Li element in the compound containing lithium ion is than for 5：4-4.6.
Described step 2) and 5) in calcining step, it is two-section calcining；
First paragraph calcining heat is 400-500 DEG C, and the time is 1-5 hour, concretely 4 hours；
Second segment calcining heat is 600-800 DEG C, concretely 700 DEG C, and the time is 5-30 hour, and concretely 15 is little
When；
The atmosphere of calcining is inertia or reducing atmosphere, is chosen in particular from nitrogen, argon gas, the gaseous mixture being made up of hydrogen and argon gas
With any one in the gaseous mixture being made up of nitrogen and hydrogen, can be more specifically by volume ratio be 5:95 hydrogen and argon gas group
The gaseous mixture becoming.
The thickness of described carbon-coating can realize precise control in 1～100nm, specially 2,2.5,3.3,3-4,5-6,9-
10th, 15-16,18-20,45-50 or 1-100nm.
The controllable thickness carbon coating method that the present invention provides, is using phenolic resin as carbon source, by sending out between phenol and aldehyde
Raw condensation polymerization reaction, grows one layer of phenolic resin polymerization in lithium ion battery electrode material or its presoma surface in situ
Thing.The electrode material of cladding novalac polymer is processed through high temperature sintering in the tube furnace be connected with reducibility gas.
The persursor material of cladding novalac polymer is first mixed with the compound containing lithium ion and is fully ground, then be connected with
Process through high temperature sintering in the tube furnace of reducibility gas.By initial feed phenol and the electrode used therein material of telo merization
Material pole material or the consumption of its presoma, and change the time of polymerisation, the thickness being coated can be in 1-100nm scope
Interior precise control.
The method controlled cladding of carbon-coating being carried out to lithium ion battery electrode material using phenolic resin home position polymerization reaction.?
The coated with carbon bed thickness arriving is uniform, distribution is controlled, carries out system research and optimization beneficial to electrode material performance.
The method is simple to operate, (includes normal temperature, heating and high-temperature solvent heat) and all can carry out under different reaction temperatures
Carbon coating.The method can carry out the homogeneous and controlled in situ cladding carbon-coating of thickness in each li-ion electrode materials particle surface.
The material carrying out after carbon coating through the method has good electric conductivity, on the one hand solves polyanionic positive electrode electricity
Conductance is low, the defect of high rate performance difference, on the other hand also can limit some negative materials (such as Si, SnO2, TiO2Deng) in charge and discharge
Producing the powdered leading to due to huge Volume Changes in electric process, thus improving the capacity of material, improving cycle performance
And security.By regulating and controlling to thickness, the chemical property (high rate performance and cycle performance) of material can be carried out excellent
Change, determine optimal carbon coating thickness and optimal chemical property.
Brief description
Fig. 1 is according to the LiFePO prepared by embodiment 14The TEM figure of@C sample, carbon coating thickness is 2nm.
Fig. 2 is according to the LiFePO prepared by embodiment 24The TEM figure of@C sample, carbon coating thickness is 3.3nm.
Fig. 3 is according to the LiFePO prepared by embodiment 34The TEM figure of@C sample, carbon coating thickness is 5nm.
Fig. 4 is according to the LiFePO prepared by embodiment 44The TEM figure of@C sample, carbon coating thickness is 8.5nm.
Fig. 5 is according to the LiFePO prepared by embodiment 54The TEM figure of@C sample, carbon coating thickness is 16nm.
Fig. 6 is according to the LiFePO prepared by embodiment 64The TEM figure of@C sample, carbon coating thickness is 50nm.
Fig. 7 is according to intermediate product a and LiFePO prepared by embodiment 34The XRD comparison diagram of@C sample.
Fig. 8 is the LiFePO as prepared by embodiment 2-54High rate performance after@C sample is assembled into button cell compares
Figure.
Fig. 9 is the LiFePO as prepared by embodiment 34@C sample and pure LiFePO4Charge and discharge first under 0.1C multiplying power
Electric curve map.
Figure 10 is the standby LiFePO of the ownership4@C sample be assembled into button cell after ac impedance spectroscopy comparison diagram.
Figure 11 is according to the LiFePO prepared by embodiment 34The cycle performance figure of@C sample button cell.
Figure 12 is according to the LiFePO prepared by embodiment 34@C sample and pure LiFePO4Raman spectrogram.
Figure 13 is according to the LiMn prepared by embodiment 70.5Fe0.5PO4The TEM of@C sample schemes, and carbon coating thickness is
2.5nm.
Figure 14 is according to the LiMn prepared by embodiment 80.5Fe0.5PO4The TEM figure of@C sample, carbon coating thickness is 5nm.
Figure 15 is according to the LiMn prepared by embodiment 90.5Fe0.5PO4The TEM figure of@C sample, carbon coating thickness is 10nm.
Figure 16 is according to the LiMn prepared by embodiment 100.5Fe0.5PO4The TEM figure of@C sample, carbon coating thickness is about
20nm.
Figure 17 is according to intermediate product a and LiMn prepared by embodiment 80.5Fe0.5PO4The XRD comparison diagram of@C sample.
Figure 18 is to dress up the high rate performance figure after button cell according to the LMFP C2 sample sets prepared by embodiment 8.
Figure 19 is according to the LMFP@C2 sample prepared by embodiment 8 and charge and discharge first under 0.1C multiplying power for the pure LMFP
Electric curve map.
Figure 20 is according to the LMFP@C2 sample prepared by embodiment 8 and cycle performance under 0.1C multiplying power for the pure LMFP
Figure.
Figure 21 is according to the LiMnPO prepared by embodiment 114The TEM figure of@C sample, carbon coating thickness is 2-3nm.
Figure 22 is according to the LiMnPO prepared by embodiment 124The TEM figure of@C sample, carbon coating thickness is 5-6nm.
Figure 23 is according to the FePO prepared by embodiment 134The TEM figure of@RF sample, cladding thickness is 3-4nm.
Figure 24 is according to the FePO prepared by embodiment 144The TEM figure of@RF sample, cladding thickness is 8-9nm.
Figure 25 and 26 is (to be designated as MnPO according to the intermediate product prepared by embodiment 154@RF) sample TEM figure, cladding
Thickness is 25nm.
Figure 27 is (to be designated as SiO according to the intermediate product prepared by embodiment 162@RF) sample TEM figure, cladding thickness be
20nm.
Figure 28 is the TEM figure according to the Si@C sample prepared by embodiment 17, and cladding thickness is 16nm.
Figure 29 is (to be designated as TiO according to the intermediate product prepared by embodiment 182@AF) sample TEM figure, cladding thickness be
15nm.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
Method of stating is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
LiFePO used in following embodiments4Synthetic method all as follows：
By Li2CO3, FeC2O4·2H2O, NH4H2PO4Press Li with citric acid：Fe：P：Citric acid=1.0～1.2:1:1:0.5
Mixed in molar ratio uniformly, gained mixed-powder vibration at high speed ball mill ball milling 4-5 hour, the powder mixing is placed in
It is connected with the tube furnace of hydrogen-argon-mixed (5/95 volume %), calcine 10h at 700 DEG C, naturally cool to room temperature, that is, obtain
LiFePO4Positive electrode, is named as LFP.
Li Mn used in following embodiments0.5Fe0.5PO4Synthetic method all as follows：
In 500ml beaker, add 200ml tetraethylene glycol, and add 1M H3PO430ml, stirring at normal temperature is uniform.Use 1M
The pH value of above-mentioned solution is transferred to 8.5 by the LiOH aqueous solution, is subsequently adding containing 0.5M FeSO4And 0.5MMnSO4The aqueous solution
30ml, in above-mentioned mixed solution, after continuing stirring at normal temperature 30min, above-mentioned solution is proceeded to teflon-lined high pressure anti-
Answer in kettle, react 10 hours under 250 °.The celadon sediment of gained is collected by centrifugation, and cleans 3 times with water, ethanol purge
3 times, the precipitation of collection is placed in 80 DEG C of vacuum drying chamber and fully 12h is dried, and obtains LiMn0.5Fe0.5PO4Positive electrode, life
Entitled LMFP.
LiMnPO used in following embodiments4Synthetic method all as follows：
In 500ml beaker, add 150ml polyethylene glycol, and add 1M H3PO430ml, stirring at normal temperature is uniform.Use 1M
The pH value of above-mentioned solution is transferred to 12.5 by the LiOH aqueous solution, is subsequently adding the MnSO of 1M4Aqueous solution 30ml is in above-mentioned mixed solution
In, after continuing stirring at normal temperature 30min, above-mentioned solution is proceeded in teflon-lined autoclave, anti-under 150 °C
Answer 10 hours.The lightpink sediment of gained is collected by centrifugation, and is cleaned with water 3 times, ethanol purge 3 times, the precipitation of collection is put
Fully 12h is dried in 80 DEG C of vacuum drying chamber, obtains LiMnPO4Positive electrode, is named as LMP.
FePO used in following embodiments4Synthetic method all as follows：Filling single neck of 300ml deionized water
3.7g FeCl is sequentially added in flask3With 2.62g NH4H2PO4, react 4h at room temperature.Yellow mercury oxide centrifugation by gained
Collect, and cleaned with book 3 times, ethanol purge 1 time, the precipitation of collection is placed in 80 DEG C of air dry oven 12h is fully dried
Afterwards, the powder of collection is placed in Muffle furnace, calcines 2h at 500 DEG C, to remove the crystallization water being carried in powder, obtains FePO4.
Mn used in following embodiments2P2O7Synthetic method all as follows：In the single neck flask filling 80ml ethanol
Sequentially add the Mn (NO that 25ml mass concentration is 50%3)2The aqueous solution and 20ml H3PO4, in 40 ° of lower stirring reactions 2h.By institute
Khaki sediment be collected by centrifugation, and clean with water 3 times, ethanol purge 1 time, the vacuum that the precipitation of collection is placed in 80 DEG C is dry
12h is fully dried in dry case.By dried powder vibration at high speed ball mill ball milling 4-5 hour, rotating speed is 1500rpm, obtains
To MnPO4.By synthesized MnPO4Powder is placed in the tube furnace being connected with argon gas or nitrogen, calcines 4h at 600 DEG C, naturally cold
But to room temperature, and use vibration at high speed ball mill ball milling 4-5 hour more again, rotating speed is 1500rpm, that is, obtain Mn2P2O7.
SiO used in following embodiments2Synthetic method all as follows：In the single neck flask filling 100ml ethanol
Sequentially add 5ml water, 5ml ammoniacal liquor and 2ml TEOS (tetraethoxysilane), stir 4h under normal temperature, white depositions are centrifuged
Collect, and wash three times with water, ethanol is washed once, gained precipitation is placed in 80 DEG C of drying box and 12h is fully dried, that is, obtain
SiO2.
Embodiment 1, Application way a carry out carbon-coating cladding
1) weighing 1.0g (6.34mmol) granularity is 150nm positive electrode LiFePO4In in there being 30ml H2O and 15mlEtOH
Mixed solution in, ultrasonic disperse 15-30min.Then sequentially add 0.05g (0.455mmol) resorcinol pressed powder,
0.2ml mass percentage concentration is 25% ammoniacal liquor (1.30mmol) and formalin that 0.1ml mass concentration is 37%
(1.34mmol), stir 24h at room temperature.Sediment is collected by centrifugation, and is cleaned with water 3 times, ethanol purge 1 time, gained sinks
Shallow lake is placed in 80 DEG C of drying box and fully 12h is dried, and obtains intermediate product a；
2) dried powder intermediate product a (being denoted as LFP@RF) is placed in and is connected with hydrogen-argon-mixed (5/95 volume %)
In tube furnace, calcine 4h at 400 DEG C, then temperature is increased to 700 DEG C, calcine 15h, naturally cool to room temperature and obtain
LiFePO4The dusty material of@C.
Fig. 1 is LiFePO manufactured in the present embodiment4Transmission electron microscope (TEM) figure of@C sample, it can be seen that cladding
The thickness of carbon-coating is 2nm, and carbon is uniformly coated on LiFePO4Surface.This sample is denoted as LFP@C (2).
Embodiment 2, Application way a carry out carbon-coating cladding
It is with the difference of embodiment 1：
Weigh 0.9g LiFePO4(5.70mmol), and add 0.065g (0.591mmol) resorcinol pressed powder in
In reaction system.
Fig. 2 is LiFePO manufactured in the present embodiment4Transmission electron microscope (TEM) figure of@C sample, it can be seen that cladding
The thickness of carbon-coating is 3.3nm, and this sample is denoted as LFP@C (3.3).
Embodiment 3, Application way a carry out carbon-coating cladding
It is with the difference of embodiment 1：
Weigh 0.4g LiFePO4, and add 0.07g (0.636mmol) resorcinol pressed powder in anti-(2.54mmol)
Answer in system.
Fig. 3 is LiFePO manufactured in the present embodiment4Transmission electron microscope (TEM) figure of@C sample, it can be seen that cladding
The thickness of carbon-coating is 5nm, and this sample is denoted as LFP@C (5).
Fig. 7 is the XRD spectra of LFP@C sample manufactured in the present embodiment, and intermediate product LFP@RF and pure LiFePO4
And standard spectrogram is compared it can be seen that synthesized material meets standard card (JCPDS No.81-1173), orthogonal
Crystallographic system, Pnma space group.LiFePO after carbon coating4With the LiFePO coating through novalac polymer4And it is uncoated
LiFePO4Spectrogram does not have difference, shows that in the present invention, method for coating and heat treatment process are not destroyed to material itself.
Embodiment 4, Application way a carry out carbon-coating cladding
It is with the difference of embodiment 1：
Weigh 0.5g LiFePO4(3.17mmol), add 0.1g (0.909mmol) resorcinol pressed powder in reaction
In system.
Fig. 4 is LiFePO manufactured in the present embodiment4Transmission electron microscope (TEM) figure of@C sample, it can be seen that cladding
The thickness of carbon-coating is 10nm, and this sample is denoted as LFP@C (10).
Embodiment 5, Application way a carry out carbon-coating cladding
It is with the difference of embodiment 1：
Weigh 0.3g LiFePO4(1.90mmol), add 0.1g (0.909mmol) resorcinol pressed powder in reaction
In system.
Fig. 5 is LiFePO manufactured in the present embodiment4Transmission electron microscope (TEM) figure of@C sample, it can be seen that cladding
The thickness of carbon-coating is 16nm, and this sample is denoted as LFP@C (16).
Embodiment 6, Application way b carry out carbon-coating cladding
1) weigh 1.0g (6.34mmol) LiFePO4In equipped with 50ml H2The volumetric flask of O and 24ml EtOH mixed solution
In, ultrasonic disperse 15-30min.Then 1.0g (9.09mmol) resorcinol pressed powder, 0.5ml percent mass are sequentially added
Concentration is 25% ammoniacal liquor and formalin that 0.3ml mass percentage concentration is 37%, stirs 24h at room temperature.To precipitate
Thing is collected by centrifugation, and is cleaned with water 3 times, ethanol purge 1 time, and gained precipitation is placed in 80 DEG C of drying box and fully 12h is dried, and obtains
To intermediate product a；
2) in order to quickly obtain thicker carbon-coating cladding, embody the ability of THICKNESS CONTROL, the present embodiment employs secondary bag
The method covered：Powder intermediate product a0.3g dried in (1) is added to again equipped with 30ml H2O and 12ml EtOH mixes
Close in the volumetric flask of solution, ultrasonic disperse 15-30min.Sequentially add 0.4g (3.64mmol) resorcinol, 0.2ml matter again
Amount percentage concentration is 25% ammoniacal liquor and formalin that 0.2ml mass percentage concentration is 37%, stirs 24h at room temperature,
Collect precipitation, eccentric cleaning, be dried, obtain secondary intermediate product I.
3) by step 2) gained secondary intermediate product I be placed in be connected with by volume ratio be 5：95 hydrogen and argon gas composition mixed
Close in the tube furnace of gas, carry out the first section calcining 4h at 400 DEG C, then temperature is increased to 700 DEG C, carry out the second section calcining
15h, naturally cools to room temperature and obtains LiFePO4The dusty material of@C.
Fig. 6 is LiFePO manufactured in the present embodiment4Transmission electron microscope (TEM) figure of@C sample, it can be seen that cladding
The thickness of carbon-coating is about 50nm, and this sample is denoted as LFP@C (50).
From prepared LFP@C (3.3), LFP@C (5), LFP@C (8.5) and (16) four kinds of sample preparation lithium electricity of LFP@C
Pond positive pole：According to LFP@C：Conductive black：Kynoar (PVDF)=80%：10%：10% (mass ratio) is prepared into electrode.
Lithium metal is assembled into 2032 button cells for negative pole, is 2.5-4.2V (vs Li in voltage range+/ Li) in carry out constant current and fill
Discharge test.
Fig. 8 is the LiFePO of all four difference carbon coating thickness4High rate performance figure, as can be seen from Figure press embodiment
LFP@C (5) sample (carbon coating thickness is about 5nm) prepared by 2 has best high rate performance, illustrates that 5nm is used
LiFePO4Optimal carbon coating thickness.
In order to verify the advantage of homogeneous complete cladding carbon-coating, in LiFePO4A certain amount of novalac polymer of middle mixing
High rate performance through sample obtained by high temperature sintering is also found in Fig. 8 more afterwards, is denoted as LFP-C.
The synthetic method of LFP＆C is：It is added without LiFePO in embodiment 14, sequentially add 0.1g resorcinol, 0.2ml
Ammoniacal liquor and 0.1ml formaldehyde are in filling 30ml H2In the volumetric flask of O and 15ml EtOH mixed solution, under room temperature, stir 24h, centrifugation
Collect and clean, that is, obtain novalac polymer, then by gained novalac polymer according to side same as Example 1
Method and condition and LiFePO4Mixing, through stirring and high-temperature heat treatment, that is, obtains LFP-C.
From figure 7 it can be seen that comparing pure LiFePO4, the high rate performance of LFP-C also has greatly improved, but with warp
Four LFP@C sample crossing carbon-coating cladding are compared, and capacity boost amplitude is still limited.Although the addition that carbon is described is to polyanion
The effect that the performance of type positive electrode is obviously improved, but the carbon-coating of homogeneous cladding has the effect becoming apparent from, to optimizing such
The high rate performance of material has bigger meaning.
Fig. 9 is the first circle charge and discharge platform curve of LFP@C (5) sample and pure LFP sample, compares discovery through 5nm carbon
LiFePO after layer cladding4Compared with not through cladding, there is between 3.4-3.5V obvious charge and discharge platform.
Figure 10 is EIS (ac impedance spectroscopy) curve of four kinds of LFP@C sample, as can be seen from the figure through 5nm carbon-coating bag
LiFePO after covering4There is compared with the sample of other three kinds of cladding thickness the semicircle radius of minimum, explanation in medium-high frequency area
LFP@C (5) sample has the Li of minimum in the interface of active material and electrolyte+Transfer impedance, has optimum with this sample
Chemical property be consistent.
Figure 11 is the cycle performance figure of sample LFP C (5) with optimum cladding thickness (5nm), and with pure LiFePO4
Contrasted.It can be seen that the LiFePO in 50 circulations, after 5nm carbon-coating cladding4Than uncoated
LiFePO4Cycle performance there is large increase, and there is no obvious capacity attenuation.
Figure 12 is the Raman spectrogram of LFP@C (5) sample and uncoated LFP sample.Compared with pure LFP, pass through
The LFP sample of carbon-coating cladding is 1360 and 1590cm-1There is peak to occur, correspond respectively to feature D and the G of material with carbon element Raman spectrum
Peak is it was demonstrated that the presence of LFP surface semi-graphited carbon-coating after cladding.
Embodiment 7
According to the step of embodiment 1, it is with the difference of embodiment 1：
Weigh the LiMn that 1.0g granularity is 150nm0.5Fe0.5PO4, and add between 0.05g (0.455mmol) (6.36mmol)
Benzenediol is in reaction system.
Temperature calcines 4h at being 400 DEG C, then temperature is increased to 700 DEG C, calcines 15h, naturally cools to room temperature and obtain
LiMn0.5Fe0.5PO4The dusty material of@C, is named as LMFP@C1.
Figure 13 is LiMn manufactured in the present embodiment0.5Fe0.5PO4Transmission electron microscope (TEM) figure of@C sample, can from figure
Go out, the thickness of cladding carbon-coating is 2.5nm.
Embodiment 8
According to the step of embodiment 7, difference from Example 7 is：
Weighing 0.5g granularity is 150nmLiMn0.5Fe0.5PO4, and add 0.05g (0.455mmol) isophthalic (3.18mmol)
Diphenol is in reaction system.The LiMn finally giving0.5Fe0.5PO4@C sample is named as LMFP@C2.
Figure 14 is the LiMn of preparation in the present embodiment0.5Fe0.5PO4Transmission electron microscope (TEM) figure of@C sample, permissible from figure
Find out, the thickness of cladding carbon-coating is 5-6nm.
Figure 17 is the XRD spectra of LMFP@C sample manufactured in the present embodiment, and intermediate product LMFP@RF and pure
LiMn0.5Fe0.5PO4And standard spectrogram is compared it can be seen that synthesized material meets standard card (JCPDS
No.42-0580), rhombic system, pmnb space group.LiMn after carbon coating0.5Fe0.5PO4With through novalac polymer bag
The LiMn covering0.5Fe0.5PO4And uncoated LiMn0.5Fe0.5PO4Spectrogram does not have difference, again shows that bag in the present invention
Coating method and heat treatment process are not destroyed to material itself.
Embodiment 9
According to the step of embodiment 7, difference from Example 7 is：
Weighing 0.5g granularity is 150nmLiMn0.5Fe0.5PO4, and add 0.1g (0.909mmol) isophthalic (3.18mmol)
Diphenol is in reaction system.The LiMn finally giving0.5Fe0.5PO4@C sample is named as LMFP@C3.
Figure 15 is the LiMn of preparation in the present embodiment0.5Fe0.5PO4Transmission electron microscope (TEM) figure of@C sample, permissible from figure
Find out, the thickness of cladding carbon-coating is 10nm.
Embodiment 10
According to the step of embodiment 7, difference from Example 7 is：
Weighing 0.3g granularity is 150nmLiMn0.5Fe0.5PO4, and add 0.2g (1.82mmol) isophthalic two (1.91mmol)
Phenol is in reaction system.The LiMn finally giving0.5Fe0.5PO4@C sample is named as LMFP@C4.
Figure 16 is the LiMn of preparation in the present embodiment0.5Fe0.5PO4Transmission electron microscope (TEM) figure of@C sample, permissible from figure
Find out, the thickness of cladding carbon-coating is about 20nm.
Prepare lithium battery anode from prepared LMFP@C2 (cladding thickness is 5nm)：According to LMFP@C：Conductive black：
Kynoar (PVDF)=80%：10%：10% (mass ratio) is prepared into electrode.Lithium metal is assembled into 2032 buttons for negative pole
Battery, is 2.5-4.5V (vs Li in voltage range+/ Li) in carry out constant current charge-discharge test.The multiplying power of wherein charging is
0.1C, discharge-rate is 0.1C, 1C, 2C, 5C and 10C.
Figure 18 is the high rate performance figure of LMFP@C2 sample, and as can be seen from the figure after 5nm carbon-coating cladding, material shows
More excellent high rate performance is shown, the specific discharge capacity under 10C can reach 103mAh g-1.
Figure 19 is the first circle charge and discharge platform curve of LMFP@C2 sample and pure LMFP sample, does not as can be seen from the figure have
The sample through cladding is had substantially not have significant Fe and Mn platform, after 5nm carbon-coating cladding, LiMn0.5Fe0.5PO4Occur
Obvious charge and discharge platform.
Figure 20 is the cycle performance figure of LMFP@C2 sample, and carries out comparing glue with pure LMFP.It can be seen that
In 50 circulations, the LMFP@C2 after carbon-coating cladding all has in discharge capacity and cycle performance than uncoated sample
Significantly improve.
Embodiment 11
According to the step of embodiment 1, it is with the difference of embodiment 1：
Weighing 0.8g granularity is 100nm LiMnPO4(5.10mmol), and add 0.1g (0.909mmol) resorcinol in
In reaction system.
Temperature calcines 4h at being 400 DEG C, then temperature is increased to 700 DEG C, calcines 15h, naturally cools to room temperature and obtain
LiMnPO4The dusty material of@C, is named as LMP@C1.
Figure 21 is LiMnPO manufactured in the present embodiment4Transmission electron microscope (TEM) figure of@C sample, it can be seen that bag
The thickness covering carbon-coating is 2-3nm.
Embodiment 12
According to the step of embodiment 11, it is with the difference of embodiment 11：
Weighing 0.5g granularity is 100nm LiMnPO4(3.19mmol), and add 0.1g (0.909mmol) resorcinol in
In reaction system, finally give LiMnPO4The dusty material of@C, is named as LMP@C2.
Figure 22 is LiMnPO manufactured in the present embodiment4Transmission electron microscope (TEM) figure of@C sample, it can be seen that bag
The thickness covering carbon-coating is 4-5nm.
Embodiment 13
According to the step of embodiment 1, it is with the difference of embodiment 1：
1) weighing 0.3g granularity is 50nm presoma I FePO4, and add 0.1g (0.909mmol) isophthalic (1.99mmol)
Diphenol in reaction system, the FePO that the intermediate product that obtains coats for novalac polymer4Nano particle, coating thickness is
3-4nm, is named as FP@RF1, namely intermediate product b (as shown in figure 23)；
2) by gained intermediate product b FePO4@RF nano particle and LiOH are with 1:(Li is excessive for 1.05 mixed in molar ratio
5%), it is fully ground 30-60min, then the powder after grinding is placed in the tubular type being connected with hydrogen-argon-mixed (5/95 volume %)
In stove, calcine 4h at 400 DEG C, then temperature is increased to 700 DEG C, calcine 15h, naturally cool to room temperature and obtain LiFePO4@C
Dusty material, be named as LFPForerunner@C1.
Embodiment 14
According to the step of embodiment 13, it is with the difference of embodiment 13：
1) weighing 0.3g granularity is 50nm presoma I FePO4, and add 0.3g (2.73mmol) isophthalic (1.99mmol)
Diphenol in reaction system, the FePO that the intermediate product that obtains coats for novalac polymer4Nano particle, coating thickness is
3-4nm, is named as FP@RF2, namely intermediate product b (as shown in figure 24)；
2) by gained intermediate product b FePO4@RF nano particle and LiOH are with 1:(Li is excessive for 1.05 mixed in molar ratio
5%), it is fully ground 30-60min, then the powder after grinding is placed in the tubular type being connected with hydrogen-argon-mixed (5/95 volume %)
In stove, calcine 4h at 400 DEG C, then temperature is increased to 700 DEG C, calcine 15h, naturally cool to room temperature and obtain LiFePO4@C
Dusty material, be named as LFPForerunner@C2.
Embodiment 15
According to the step of embodiment 1, it is with the difference of embodiment 1：
1) weigh the presoma II Mn that 0.3g granularity is 100-300nm (1.06mmol)2P2O7, and add 0.2g
(1.82mmol) resorcinol, the Mn that the intermediate product obtaining coats for novalac polymer2P2O7Nano particle, cladding is thick
Degree is about 25nm, is named as MPO@RF (as shown in figs. 25 and 26), namely intermediate product c；
2) by gained intermediate product c Mn2P2O7@RF nano particle, LiOH and NH4H2PO4With 1:1.05:1 mol ratio is mixed
Close (Li excessive 5%), be fully ground 30-60min, then the powder after grinding is placed in and is connected with hydrogen-argon-mixed (5/95 body
Long-pending %) tube furnace in, calcine 4h at 400 DEG C, then temperature be increased to 700 DEG C, calcine 15h, naturally cool to room temperature and obtain
To LiMnO4The dusty material of@C, is named as LMPForerunner@C.
Embodiment 16
According to the step of embodiment 1, it is with the difference of embodiment 1：
1) weigh the presoma III SiO that 0.4g granularity is 250nm (6.66mmol)2, and add 0.1g (0.909mmol)
Resorcinol and 0.01g CTAB (cetyl trimethylammonium bromide), the intermediate product obtaining coats for novalac polymer
SiO2Nano particle, is named as SiO2@RF (as shown in figure 27), namely intermediate product d；
2) by gained intermediate product d SiO2@RF nano particle, iron containing compoundses FeC2O4And CH3COOLi is with 1:1:2.10
Mol ratio (wherein, FeC2O4Mole dosage in terms of wherein Fe element, CH3COOLi is in terms of Li element) (Li is excessive for mixing
5%), it is fully ground 30-60min, then the powder after grinding is placed in the tubular type being connected with hydrogen-argon-mixed (5/95 volume %)
In stove, calcine 4h at 400 DEG C, then temperature is increased to 800 DEG C, calcine 15h, naturally cool to room temperature and obtain Li2FeSiO4@C
Dusty material, LFS@C.
Embodiment 17
According to the step of embodiment 1, it is with the difference of embodiment 1：
Weigh presoma IIISi (1.78mmol) pressed powder that 0.05g granularity is 50-100nm, and add 0.2g
(1.82mmol) resorcinol is in reaction system.Finally give the Si@C sample through carbon coating.
Figure 28 is transmission electron microscope (TEM) figure of the Si@C sample of preparation in the present embodiment, it can be seen that carbon coated
The thickness of layer is 16nm.
Embodiment 18
According to the step of embodiment 1, it is with the difference of embodiment 1：
1) weigh the presoma IV TiO that 0.1g (1.25mmol) granularity is 10-30nm2Pressed powder, and add 0.1g
(0.916mmol) m-aminophenol is in reaction system, the TiO that the intermediate product obtaining coats for novalac polymer2Receive
Rice grain, is named as TiO2@AF (as shown in figure 29), namely intermediate product f；
2) by gained intermediate product f TiO2@AF nano particle and CH3COOLi is with 5:(Li is excessive for 4.12 mixed in molar ratio
3%), it is fully ground 30-60min, then the powder after grinding is placed in the tube furnace being connected with argon gas, calcines at 400 DEG C
4h, then temperature is increased to 700 DEG C, calcine 15h, naturally cool to room temperature and obtain Li4Ti5O12The dusty material of@C, LTO@C.
Claims (16)
1. a kind of method that surface to lithium ion battery electrode material carries out carbon-coating cladding, is method a or b；
Wherein, method a comprises the steps：
1) raw material is placed in the mixed liquor being made up of water and ethanol, sequentially adds phenolic compound, ammoniacal liquor and aldehyde compound
The aqueous solution stirring, collect precipitation, obtain intermediate product；
Wherein, described raw material is anode material for lithium-ion batteries or negative material；
When described raw material is positive electrode, gained intermediate product is designated as intermediate product a；
When described raw material is presoma I, gained intermediate product is designated as intermediate product b；
When described raw material is presoma II, gained intermediate product is designated as intermediate product c；
When described raw material is presoma III, gained intermediate product is designated as intermediate product d；
When described raw material is negative material, gained intermediate product is designated as intermediate product e；
When described raw material is presoma IV, gained intermediate product is designated as intermediate product f；
2) by step 1) gained intermediate product a calcined, naturally cools to room temperature, complete the cladding of described carbon-coating；Or,
By step 1) gained intermediate product b mixed with the compound containing lithium ion and calcined, naturally cool to room temperature, complete
The cladding of described carbon-coating；Or,
By step 1) gained intermediate product c mixed with the compound containing lithium ion and the ammonium salt containing phosphate radical and calcined,
Naturally cool to room temperature, complete the cladding of described carbon-coating；Or,
By step 1) gained intermediate product d, the compound containing lithium ion and iron containing compoundses mixing calcined, natural cooling
To room temperature, complete the cladding of described carbon-coating；
By step 1) gained intermediate product e calcined, naturally cools to room temperature, complete the cladding of described carbon-coating；Or,
By step 1) gained intermediate product f mixed with the compound containing lithium ion and calcined, naturally cool to room temperature, complete
The cladding of described carbon-coating；
Method b comprises the steps：
3) raw material is placed in the mixed liquor being made up of water and ethanol, sequentially adds phenolic compound, ammoniacal liquor and aldehyde compound
The aqueous solution stirring, collect precipitation, obtain intermediate product；
Wherein, described raw material is anode material for lithium-ion batteries or negative material；
When described raw material is positive electrode, gained intermediate product is designated as intermediate product a；
When described raw material is presoma I, gained intermediate product is designated as intermediate product b；
When described raw material is presoma II, gained intermediate product is designated as intermediate product c；
When described raw material is presoma III, gained intermediate product is designated as intermediate product d；
When described raw material is negative material, gained intermediate product is designated as intermediate product e；
When described raw material is presoma IV, gained intermediate product is designated as intermediate product f；
4) by step 3) gained intermediate product is placed in the mixed liquor being made up of water and ethanol, sequentially adds phenolic compound, ammonia
The aqueous solution stirring of water and aldehyde compound, collects precipitation, obtains secondary intermediate product；
Wherein, when described intermediate product is intermediate product a, the secondary intermediate product of gained is designated as secondary intermediate product I；
When described intermediate product is intermediate product b, the secondary intermediate product of gained is designated as secondary intermediate product II；
When described intermediate product is intermediate product c, the secondary intermediate product of gained is designated as secondary intermediate product III；
When described intermediate product is intermediate product d, the secondary intermediate product of gained is designated as secondary intermediate product IV；
When described intermediate product is intermediate product e, the secondary intermediate product of gained is designated as secondary intermediate product V；
When described intermediate product is intermediate product f, the secondary intermediate product of gained is designated as secondary intermediate product VI；
5) by step 4) gained secondary intermediate product I calcined, and naturally cools to room temperature, completes described carbon-coating cladding；Or,
By step 4) gained secondary intermediate product II mixed with the compound containing lithium ion and calcined, and naturally cools to room
Temperature, completes described carbon-coating cladding；Or,
By step 4) gained secondary intermediate product III, the compound containing lithium ion and the ammonium salt containing phosphate radical mixing carry out
Calcining, naturally cools to room temperature, completes described carbon-coating cladding；Or,
By step 4) gained secondary intermediate product IV, the compound containing lithium ion and iron containing compoundses mixing calcined, from
So it is cooled to room temperature, complete described carbon-coating cladding；
By step 4) gained secondary intermediate product V calcined, and naturally cools to room temperature, completes described carbon-coating cladding；Or,
By step 4) gained secondary intermediate product VI mixed with the compound containing lithium ion and calcined, and naturally cools to room
Temperature, completes described carbon-coating cladding；
The formula of described positive electrode is LixMXO4；
Wherein, M is transition metal；Described M is selected from least one in Fe, Mn, V, Co and Ni；
X is phosphorus, silicon or sulphur；
0<x<2；
Described negative material is selected from Si, SnO2、TiO2And Li4Ti5O12In at least one；
Described presoma I is FePO4、Fe3(PO4)2,MnPO4、Mn3(PO4)2Or Mn1-xFexPO4；Described Mn1-xFexPO4In, 0<x
<1；
Described presoma II is Fe2P2O7、Mn2P2O7Or (Mn1-xFex)2P2O7；Described Mn1-xFexPO4In, 0<x<1；
Described presoma III is Si or SiO2；
Described presoma IV is TiO2.
2. method according to claim 1 it is characterised in that：The grain graininess of described positive electrode and negative material is
50nm-1μm；
The grain graininess of described presoma I, II, III and IV is 10-500nm；
Described step 1), 3) and 4) in, described phenolic compound be phenol derivatives；
Described aldehyde compound is selected from least one in formaldehyde, acetaldehyde, propionic aldehyde and glutaraldehyde；
The mass percentage concentration of the aqueous solution of described aldehyde compound is 10-40%.
3. method according to claim 1 it is characterised in that：Described positive electrode is selected from LiFePO4、LiMnPO4、
LiMn1-xFexPO4、Li3V2(PO4)3、Li2FeSiO4、LiCoPO4And LiNiPO4In at least one；Described LiMn1-xFexPO4
In, 0<x<1.
4. method according to claim 2 it is characterised in that：Described phenol derivatives is the phenol containing substituent, its
In, described substituent is selected from the alkyl of C1-C5, amino, the aminoalkyl of C1-C5, hydroxyl, sulfydryl, nitro, sulfonic group, C1-C5
At least one in the alkoxyl of carboxyl, halogen and C1-C5.
5. method according to claim 4 it is characterised in that：The described phenol containing substituent is selected from methylphenol, benzene
At least one in diphenol, benzenetriol, amino-phenol and nitrophenol.
6. method according to claim 5 it is characterised in that：Described methylphenol is ortho-methyl phenol, m-methyl phenol
Or p-methyl phenol；Described benzenediol is catechol, resorcinol or hydroquinones；Described benzenetriol is 1,2,3- benzene three
Phenol, oxyhydroquinone or phloroglucin；Described amino-phenol is o-aminophenol, m-aminophenol or para-aminophenol；Institute
State nitrophenol be ortho position, meta, contraposition replace nitrophenol.
7. method according to claim 2 it is characterised in that：Described phenol derivatives is naphthols.
8. method according to claim 2 it is characterised in that：The mass percentage concentration of the aqueous solution of described aldehyde compound
For 30-40%.
9. method according to claim 8 it is characterised in that：The mass percentage concentration of the aqueous solution of described aldehyde compound
For 37%.
10. the method according to any one of claim 1-9 it is characterised in that：Described step 1), 3) and 4) in, described by
In the mixed liquor of water and ethanol composition, the volume ratio of water and ethanol is 0.5-50：1；
The mass percentage concentration of described ammoniacal liquor is 25-28%；
Described step 1) and 3) in, the mole dosage of raw material, phenolic compound, aldehyde compound and ammoniacal liquor is than for 0.1-60：
0.05-30：0.05-30：0.5-15；
Described step 4) in, the mole dosage of secondary intermediate product, phenolic compound, aldehyde compound and ammoniacal liquor is than for 0.1-
60：0.05-30：0.05-30：0.5-15.
11. according to the arbitrary described method of claim 1-9 it is characterised in that：Described step 1), 3) and 4) in whipping step,
Temperature is 20-200 DEG C, and the time is 0.3-48 hour.
12. according to the arbitrary described method of claim 1-9 it is characterised in that：Described step 2) and 5) in, described containing lithium from
The compound of son is lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate, lithium sulfate, lithium dihydrogen phosphate, lithium oxalate, lithium formate, silicon
Sour lithium, lithium laurate, lithium citrate or malic acid lithium；
The described ammonium salt containing phosphate radical is diammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium phosphate；
Described iron containing compoundses are ferrous oxalate, iron chloride, ferric nitrate, ferrous sulfate, acetylacetone,2,4-pentanedione are ferrous or ferric acetyl acetonade.
13. according to the arbitrary described method of claim 1-9 it is characterised in that：Described step 2) in, intermediate product b with contain
In the compound of lithium ion, the mole dosage that feeds intake of Li element is than for 1：1.0-1.2；
In Li element and the ammonium salt containing phosphate radical in described intermediate product c, the compound containing lithium ion, feeding intake of P element is rubbed
Your amount ratio is 1：1.0-1.2：1；
In Li element and iron containing compoundses in described intermediate product d, the compound containing lithium ion Fe element feed intake mole with
Amount ratio is 1：2.0-2.4：1；
In described intermediate product f, the compound containing lithium ion, the mole dosage that feeds intake of Li element is than for 5：4-4.6；
Described step 5) in, secondary intermediate product II with the mole dosage ratio that feeds intake of Li element in the compound containing lithium ion is
1：1.0-1.1；
In Li element and the ammonium salt containing phosphate radical in secondary intermediate product III, the compound containing lithium ion, P element feeds intake
Mole dosage is than for 1：1.0-1.2：1；
In Li element and iron containing compoundses in secondary intermediate product IV, the compound containing lithium ion Fe element feed intake mole with
Amount ratio is 1：2.0-2.4：1；
The mole dosage that feeds intake of secondary intermediate product VI and Li element in the compound containing lithium ion is than for 5：4-4.6.
14. according to the arbitrary described method of claim 1-9 it is characterised in that：Described step 2) and 5) in calcining step, be
Two-section calcining；
First paragraph calcining heat is 400-500 DEG C, and the time is 1-5 hour；
Second segment calcining heat is 600-800 DEG C, and the time is 5-30 hour；
The atmosphere of calcining is inertia or reducing atmosphere.
15. methods according to claim 14 it is characterised in that：The atmosphere of described calcining be selected from nitrogen, argon gas, by hydrogen
Any one in the gaseous mixture be made up of with the gaseous mixture of argon gas composition and nitrogen and hydrogen.
16. according to the arbitrary described method of claim 1-9 it is characterised in that：The thickness of described carbon-coating is 1～100nm.
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