CN110233246A - Carbon coating contains composite anode active material of LiFePO4 and preparation method thereof and the application in negative electrode of lithium ion battery - Google Patents
Carbon coating contains composite anode active material of LiFePO4 and preparation method thereof and the application in negative electrode of lithium ion battery Download PDFInfo
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- CN110233246A CN110233246A CN201810182673.1A CN201810182673A CN110233246A CN 110233246 A CN110233246 A CN 110233246A CN 201810182673 A CN201810182673 A CN 201810182673A CN 110233246 A CN110233246 A CN 110233246A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses the composite anode active material and preparation method thereof that carbon coating contains LiFePO4, the method achieve LiFePO4 and conventional anode material (silica-base material or lithium titanate) be blended and the polymerization and cladding of carbon source.Carbon-coated LiFePO 4 for lithium ion batteries and conventional anode material, pass through the synergistic effect between each component, improve the problem of cyclical stability existing for conventional anode material is poor, capacity is low and poorly conductive, obtains the composite negative pole material with low volume expansion, Gao Shouci coulombic efficiency, height ratio capacity, high circulation stability and excellent high rate performance.Preparation method is simple and safety non-pollution for composite negative pole material, and cost of material is low, is suitble to industrial scale production, has good practical application foreground.
Description
Technical field:
The present invention relates to technical field of lithium ion, and in particular to a kind of carbon coating contains the composite negative pole of LiFePO4
Active material and preparation method thereof and application in negative electrode of lithium ion battery.
Background technique:
Emerged so far from 1991, commercial Li-ion battery because have stored energy capacitance is big, safety is good, it is environmental-friendly,
The advantages that self-discharge rate is low and memory-less effect, has been widely used in portable electronic product, electric car and aerospace
Equal fields.With the update of electronic product and the development of new-energy automobile, capacity and use of the people to lithium ion battery
Life requirements is higher and higher, this just needs constantly to improve the performance of each building block of lithium ion battery, especially to positive and negative
The optimization and improvement of pole material.However traditional carbon negative pole material is difficult to meet the need of power battery high-energy density and safety
It asks, researches and develops the research hotspot that new negative electrode material is lithium-ion-power cell.Currently, global lithium ion battery market competition is abnormal
Fierceness, lithium battery industry will be faced with various challenges and opportunity, and carrying out critical material technological reserve is that promotion industry is competing
Strive the key point of power.
Compared with graphite cathode material, the energy density of silicon based anode material is with the obvious advantage, and theoretical energy density is more than
10 times of graphite cathode material, up to 4200mAh/g.But silica-base material is during slotting lithium and de- lithium that there is huge
Volume change (300%), is easy to cause the dusting and peeling of electrode material, the initial coulomb efficiency of battery and cyclical stability compared with
Difference；In addition, the lower electron conduction of silica-base material and be also to restrict its commercial applications with the compatibility of conventional electrolysis liquid
An important factor for.Currently, nanometer SiClx, the sub- silicon of oxidation, silicon alloy and silicon based composite material have been carried out compared with in-depth study,
Especially silicon-carbon composite cathode material combines the advantages of silicon and carbon negative pole material, can promote the energy density of material but also change
The cyclical stability of kind material, thus it is more and more of interest by lithium electrical domain.The development and application of silicon-carbon cathode, abroad just
Step realizes industrialization, and prediction The Next 3-5 Years are promoted with permeability, and the market space that silicon-carbon cathode can possess is about 5,000,000,000
Left and right.
Lithium titanate (LTO) has been applied in actual production as the negative electrode material of power battery, it has the following excellent
Gesture: (1) stable circulation performance is strong, repeatedly circulation after capacity basically no attenuation；(2) discharge platform is steady and high, up to 1.55V；(3)
As " zero strain material ", Li+ has good migration in material lattice.But intrinsic insulating properties seriously limits
Its high rate capability, lower lithium storage content are also unfavorable for application of the LTO in real life.By modified and compound, mention
The specific capacity and lithium ion diffusion rate of high material are the hot spots studied at this stage.
LiFePO4(LFP) it is used as a kind of common anode material for lithium-ion batteries, there is cheap, nontoxic, environment phase
Capacitive is good, higher specific capacity (170mAh/g) and higher operating voltage, have extended cycle life, high-temperature behavior and has a safety feature
The advantages that.
Summary of the invention:
The object of the present invention is to provide the composite anode active materials that carbon coating contains LiFePO4, realize LiFePO4
With silica-base material or lithium titanate be blended and the polymerization and cladding of carbon source, LiFePO4 are blended with silica-base material and can effectively improve
The electrochemical cycle stability of negative electrode material, LiFePO4 is blended with lithium titanate can effectively improve lithium storage content, by simple
Carbon coating make composite anode active material have low volume expansion, Gao Shouci coulombic efficiency, height ratio capacity, high circulation stability with
And excellent high rate performance.
The present invention is achieved by the following technical programs:
Carbon coating contains the composite anode active material of LiFePO4, carries out carbon packet by LiFePO4 and conventional anode material
It is mixed after covering, including two kinds of complex methods:
One one step of mixture formed for LiFePO4 (LFP) and conventional anode material carries out carbon coating simultaneously, obtains carbon
Coat the composite cathode material for lithium ion cell of (LiFePO4/conventional anode material)；
Two carry out carbon coating respectively for LiFePO4 (LFP) and conventional anode material after remix to obtain carbon coating ferric phosphate
The mixture of lithium (LFP) and carbon coating conventional anode material, wherein in mixture, carbon-coated LiFePO 4 for lithium ion batteries and carbon coating are conventional
The ratio of negative electrode material is adjustable；
The conventional anode material is selected from any one of silica-base material (Si), lithium titanate (LTO).
One step of mixture of LiFePO4 (LFP) and conventional anode material composition carries out carbon coating preparation carbon coating simultaneously
In the composite cathode material for lithium ion cell of (LiFePO4/conventional anode material), LiFePO4 (LFP) and conventional anode material
Mass ratio be 1:100~100:1, preferably 1:6-3:4, most preferably 2:5.
The silica-base material is selected from appointing for one or more of silicon powder, the sub- silicon of oxidation, silicon-base alloy, silicon-carbon composite construction
Meaning combination.
The progress carbon coating refers to LiFePO4 (LFP), conventional anode material isoreactivity material cladding different carbon source forerunner
Then body passes through heat treatment carbonization.
The carbon source presoma is selected from 3,4- ethylenedioxy thiophene (EDOT), aniline, pyrroles, glucose, pitch, polypropylene
Any one of nitrile, graphite and graphene.
When carbon source presoma is selected from 3,4-ethylene dioxythiophene (EDOT), aniline, Bi Kashi, LiFePO4 (LFP) and normal
One step of mixture of rule negative electrode material composition carries out carbon coating simultaneously, obtains carbon coating (LiFePO4/conventional anode material)
Composite cathode material for lithium ion cell the preparation method is as follows: weighing carbon source, LiFePO4 and conventional anode material (silica-base material
Or lithium titanate), it is dispersed in deionized water, is placed in ball grinder that ball milling mixing is uniform under inert protective atmosphere；Then, will
Organic polymer polymerization initiator be added in ball grinder, under an inert atmosphere continue ball milling polymerization, reaction product through filtering,
Obtaining filter residue is presoma；Finally, by presoma, 600-800 DEG C of high temperature cabonization, cooling are obtained under an inert atmosphere.It is described organic
The initiator of high molecular polymerization is (NH4)2S2O8Or (NH4)2S2O8/Fe2(SO4)3Or FeCl3·6H2O。
When carbon source presoma is selected from 3,4-ethylene dioxythiophene (EDOT), it is also added with kayexalate.
When carbon source presoma is glucose, one step of mixture of LiFePO4 (LFP) and conventional anode material composition is same
Shi Jinhang carbon coating obtains the preparation of the composite cathode material for lithium ion cell of carbon coating (LiFePO4/conventional anode material)
Method is as follows: weighing glucose, LiFePO4 and conventional anode material (silica-base material or lithium titanate), its ultrasonic disperse is being gone
Mixed serum is obtained in ionized water；Mixed serum is then moved on into hydrothermal reaction kettle, under argon atmosphere and stirring condition
Hydro-thermal reaction, cooling, suction filtration obtains presoma；Then, the 700-800 DEG C of carbonization under argon atmosphere by presoma, it is cooling
After obtain.
When carbon source presoma is selected from pitch, polyacrylonitrile, graphite and graphene, LiFePO4 (LFP) and conventional anode
One step of mixture of material composition carries out carbon coating simultaneously, obtains the lithium ion of carbon coating (LiFePO4/conventional anode material)
Battery composite cathode material the preparation method is as follows: first in a solvent by carbon source dispersion, LiFePO4 and conventional negative is then added
Material (silica-base material or lithium titanate) ball milling in pole mixes, and product is filtered, and obtains filter residue 600-800 DEG C under argon atmosphere
Carbonization obtains.
The preparation method of carbon coating conventional anode material refers to the lithium ion of carbon coating (LiFePO4/conventional anode material)
The preparation method of battery composite cathode material, difference are that active material only has conventional anode material silica-base material or lithium titanate,
It does not include LiFePO4.
The preparation method of carbon-coated LiFePO 4 for lithium ion batteries (LFP) with reference to carbon coating (LiFePO4/conventional anode material) lithium from
The preparation method of sub- battery composite cathode material, difference are that active material only has LiFePO4 silicon, do not include conventional anode material
Material.
The present invention also protects a kind of composite negative plate of lithium ion battery, comprising the composite anode active material, also
Including conductive agent and binder.
The preparation method of the composite negative plate of the lithium ion battery, comprising the following steps: composite negative pole activity material is added
Material, conductive agent, adhesive dispersions prepare uniform fluid slurry by grinding or high speed machine stirring；By what is obtained
Fluid slurry is by obtaining lithium ion battery composite cathode piece after being coated with, dry, rolling.
The present invention also protects a kind of lithium ion battery, the composite negative plate containing the lithium ion battery.
Beneficial effects of the present invention are as follows:
(1) the present invention provides a kind of new composite cathode material for lithium ion cell and preparation method thereof.
(2) present invention realizes blending and the macromolecule of LiFePO4 and silica-base material or lithium titanate using straightforward procedure
The polymerization of carbon material coats, and by high temperature cabonization, is prepared for the sandwich with polynary synergistic effect.
(3) present invention is carried out using the synergistic effect between LiFePO4, carbon material and silica-base material or lithium titanate each component
Have complementary advantages, improve the chemical property of composite material, the lithium ion battery composite cathode active material prepared has low
Volume expansion, Gao Shouci coulombic efficiency, height ratio capacity, high circulation stability and excellent high rate performance and safety non-pollution etc.
Advantage provides effectively approach for the research of high-capacity lithium ion cell.
(4) being formed when carbon source is heterocyclic compound in the present invention, after polymerization has the carbon coating of the miscellaneous element dopings such as N, S multiple
Condensation material effectively improves the coulombic efficiency for the first time of composite cathode material for lithium ion cell.
(5) present invention is easy to operate, environmentally protective, low in cost using method.
Detailed description of the invention:
Fig. 1 is the lithium ion battery composite cathode active material system of the sulfur doping carbon coating (LiFePO4/silicon) of embodiment 1
The chemical property figure of standby cathode half-cell；
Fig. 2 is the cycle performance comparison of the cathode half-cell of difference Si/LFP mass ratio in embodiment 2-4 and comparative example 1
Figure；Wherein, NS refers to that it is 70/0/20/10 that sub- silicon, LiFePO4, acetylene black, CMC mass ratio are aoxidized in pole piece；S60L10 refers to pole piece
The sub- silicon of middle oxidation, LiFePO4, acetylene black, CMC mass ratio are 60/10/20/10；S50L20, which refers to, aoxidizes sub- silicon, phosphoric acid in pole piece
Iron lithium, acetylene black, CMC mass ratio are 50/20/20/10；S40L30, which refers to, aoxidizes sub- silicon, LiFePO4, acetylene black, CMC in pole piece
Mass ratio is 40/30/20/10.
Fig. 3 is the charge and discharge that lithium ion battery composite cathode active material prepares cathode half-cell in the embodiment of the present invention 5
Curve graph.
Fig. 4 is the cathode half-cell 1-5 circle that in the embodiment of the present invention 5 prepared by lithium ion battery composite cathode active material
Cyclic voltammetry curve figure.
Fig. 5 is 6 chinese raw materials Si and LFP of the embodiment of the present invention, presoma SLP and carbon coating silicon/LiFePO4 composite wood
Expect the XRD diagram of SLC.
Fig. 6 be 6 chinese raw materials (a) Si of the embodiment of the present invention, (b) LFP and (c) presoma SLP and (d) carbon coating silicon/
The SEM of composite ferric lithium phosphate material SLC schemes
Fig. 7 is that carbon coating silicon/composite ferric lithium phosphate material SLC EDS schemes in embodiment 6.
Fig. 8 is the SC composite material of raw material LFP of the present invention and comparative example 2, the LC composite material of comparative example 3 and implementation
The cycle performance comparison diagram of the SCLC composite material of presoma SLP and SLC composite material, the preparation of embodiment 7 prepared by example 6.
Fig. 9 is the cycle performance pair of the SLC cathode half-cell for preparing in the embodiment of the present invention 6 under different high current densities
Than figure.
Figure 10 is the high rate performance figure of the SLC cathode half-cell prepared in the embodiment of the present invention 6.
Figure 11 is the charging and discharging curve figure that the embodiment of the present invention 8 prepares cathode half-cell.
Figure 12 is the cycle performance figure that cathode half-cell is prepared in the embodiment of the present invention 9.
Figure 13 is the TG figure of active material prepared by comparative example 4, comparative example 5 and embodiment 10 of the present invention.
Figure 14 is the SEM figure of the active material prepared in the embodiment of the present invention 10.
Figure 15 is the charging and discharging curve figure that embodiment 10 prepares cathode half-cell.
Figure 16 is the electrochemical impedance spectrogram that cathode half-cell is prepared in the embodiment of the present invention 12.
Figure 17 is the SEM figure of the active material prepared in the embodiment of the present invention 14.
Figure 18 is the charging and discharging curve figure that embodiment 14 prepares cathode half-cell.
Figure 19 is 16 first charge-discharge curve graph of embodiment.
Figure 20 is the cycle performance figure that the embodiment of the present invention 16 and business lithium titanate prepare cathode half-cell, wherein LTO/
LFP/C refers to embodiment 16, and LTO refers to business lithium titanate.
Specific embodiment:
Explanation is further expalined to the present invention combined with specific embodiments below, the description thereof is more specific and detailed, but
It cannot be construed as a limitation to the scope of the present invention, as long as the form using equivalent substitution or equivalent transformation is obtained
The technical solution obtained should all include within the scope of protection of the claims of the present invention.
The raw material used in following embodiment and comparative example is marketable material if not otherwise indicated.
The preparation of all composite anode active material pole pieces and battery in following embodiment and comparative example: by what is be prepared
Carbon coating (LiFePO4/silicon or lithium titanate) lithium ion battery composite cathode active material and acetylene black, bonding agent carboxymethyl are fine
Element sodium (CMC) 7:2:1 in mass ratio mixing is tieed up, appropriate amount of deionized water is added and stirs evenly, be applied on copper foil, is dried in vacuum
It is dried at 60 DEG C in case, obtains composite electrode piece in sheet-punching machine top shear blade.The electrode obtained is done into cathode, metal lithium sheet is positive
Pole, electrolyte are 1M LiPF6/EC:DEC:DMC (v:v:v=1:1:1) (10%FEC additive), and diaphragm is capillary polypropylene
Film (Celgard2400) is assembled into 2025 type button cells in the glove box full of argon gas.Have with the new Weir electronics in Shenzhen
Limit company BTS51800 battery test system, model CT-3008W are (compound containing lithium titanate in 0.01~1.5V voltage range
Material voltage window is 0.5~3V) carry out charge-discharge test under 0.4~10A/g current density.
Embodiment 1:
It weighs 0.5g and aoxidizes sub- nano silicon particles, 0.12g LiFePO4,0.25g 3,4- ethylenedioxy thiophene and 0.82g
Kayexalate is dispersed in 10ml deionized water, is placed in ball grinder ball milling 2h under inert protective atmosphere and is mixed
Uniformly.Then, by 0.7g (NH4)2S2O8/6mg Fe2(SO4)3It is added in ball grinder, ball milling polymerize under inert protective atmosphere
46h obtains reaction product.Then, reaction product being filtered, filter residue successively uses water and dehydrated alcohol as cleaning solvent,
Each washing 3 times obtains presoma 60 DEG C of drying in vacuum drying oven.Presoma is carbonized under inert protective atmosphere in 600 DEG C
5h obtains the lithium ion battery composite cathode active material of sulfur doping carbon coating (LiFePO4/silicon) after cooling.
By the sulfur doping carbon coating being prepared (LiFePO4/silicon) lithium ion battery composite cathode active material and acetylene
Black, binder sodium carboxymethylcellulose (CMC) 7:2:1 in mass ratio mixing, adds appropriate amount of deionized water and stirs evenly, be coated with
It onto copper foil, is dried at 60 DEG C in vacuum drying oven, obtains composite electrode piece in sheet-punching machine top shear blade.The electrode obtained is done
Cathode, metal lithium sheet are anode, and electrolyte is 1M LiPF6/EC:DEC:DMC (v:v:v=1:1:1) (10%FEC additive),
Diaphragm is microporous polypropylene membrane (Celgard 2400), is assembled into 2025 type button cells in the glove box full of argon gas.With
The new Weir Electronics Co., Ltd. BTS51800 battery test system in Shenzhen, model CT-3008W, in 0.01~1.5V voltage
(voltage window containing lithium titanate composite material is 0.5~3V) carries out charge-discharge test under 0.4~10A/g current density in range.
Chemical property is as shown in Figure 1, specific discharge capacity still reaches 1277mAh/g, circulation 5 after 70 circle of composite anode active material circulation
After secondary, the coulombic efficiency of every circle is positively retained at 98.5% or more, and there is high coulombic efficiency for the first time, height ratio capacity, high circulation to stablize
Property.
Embodiment 2-4:
Reference implementation example 1, the difference is that LiFePO4 and the mass ratio for aoxidizing sub- silicon are respectively 1/6,2/5,3/
4。
Comparative example 1:
Reference implementation example 1, the difference is that the quality of LiFePO4 is 0.
Carbon coating (LiFePO4/silicon) lithium ion battery composite cathode that embodiment 2-4 and comparative example 1 are prepared is living
Property material is mixed with different Si/LFP mass ratioes from acetylene black, binder sodium carboxymethylcellulose (CMC) 7:2:1 in mass ratio
Pole piece, i.e. carbon coating (LiFePO4/silicon) lithium ion battery composite cathode that embodiment 2-4 and comparative example 1 are prepared is living
Property material in oxidation Asia silicon, LiFePO4 and acetylene black, CMC respectively in mass ratio be respectively 60/10/20/10,50/20/
20/10,40/30/20/10,70/0/20/10 mixing, adds appropriate amount of deionized water and stirs evenly, be applied on copper foil, true
It is dried at 60 DEG C in empty baking oven, S60L10, S50L20, S40L30 and NS electrode slice can be obtained respectively in sheet-punching machine top shear blade.It will
The electrode obtained does cathode, and metal lithium sheet is anode, and electrolyte is 1M LiPF6/EC:DEC:DMC (v:v:v=1:1:1) (10%
FEC additive), diaphragm is microporous polypropylene membrane (Celgard 2400), is assembled into 2025 types in the glove box full of argon gas
Button cell.With the new Weir Electronics Co., Ltd. BTS51800 battery test system in Shenzhen, model CT-3008W, 0.01
Charge-discharge test under 0.4A/g current density is carried out in~1.5V voltage range.As a result as shown in Figure 2.It can be seen that from figure with pole
The discharge capacity for the first time of the increase of LFP component in piece, composite pole piece reduces, but in circulation later, the stabilization of composite pole piece
Property stablize than pure silicon pole piece, and S50L20 pole piece shows optimal electrochemistry capacitance and stability.
A kind of embodiment 5: embodiment of the composite cathode material for lithium ion cell of carbon coating (LiFePO4/silicon)
Weigh 0.4g nano silicon particles, 0.16g LiFePO4,0.25g 3,4- ethylenedioxy thiophene and 0.82g polyphenyl second
Alkene sodium sulfonate is dispersed in 10ml deionized water, is placed in ball grinder ball milling 2h under inert protective atmosphere and is uniformly mixed.With
Afterwards, by 0.7g (NH4)2S2O8/6mg Fe2(SO4)3It is added in ball grinder, ball milling polyase 13 4h, obtains under inert protective atmosphere
To reaction product.Then, reaction product is filtered, filter residue successively uses water and dehydrated alcohol as cleaning solvent, respectively washs 3
It is secondary, obtain presoma 60 DEG C of drying in vacuum drying oven.It is cooling by presoma in 700 DEG C of carbonization 4h under inert protective atmosphere
The lithium ion battery composite cathode active material of sulfur doping carbon coating (LiFePO4/silicon) is obtained afterwards.
Fig. 3 and Fig. 4 is 5 sulfur doping carbon coating silicon of embodiment/LiFePO4 lithium ion battery composite cathode activity respectively
The charging and discharging curve and cyclic voltammetry curve of material.It can be seen that pole piece has an apparent electric discharge in low potential for the first time in circulation
Platform, it is corresponding with the peak of CV curve.In addition, pole piece is since the 2nd circulation, charging and discharging curve is consistent substantially, is shown
Material has good structural stability.
A kind of embodiment 6: implementation of the composite cathode material for lithium ion cell of carbon coating (LiFePO4/silicon or lithium titanate)
Example
Weigh 0.2g nano silicon particles, 0.08g LiFePO4,0.25g 3,4- ethylenedioxy thiophene and 0.82g polyphenyl second
Alkene sodium sulfonate is dispersed in 10ml deionized water, is placed in ball grinder ball milling 2h under inert protective atmosphere and is uniformly mixed.With
Afterwards, by 0.7g (NH4)2S2O8/6mg Fe2(SO4)3It is added in ball grinder, ball milling polymerize 22h under inert protective atmosphere, obtains
To reaction product.Then, reaction product is filtered, filter residue successively uses water and dehydrated alcohol as cleaning solvent, respectively washs 3
It is secondary, obtain presoma (SLP) 60 DEG C of drying in vacuum drying oven.By presoma in 800 DEG C of carbonization 3h under inert protective atmosphere,
The lithium ion battery composite cathode active material SLC of sulfur doping carbon coating (LiFePO4/silicon) is obtained after cooling.Fig. 5, shown in 6
Respectively the present embodiment raw material nano Si, LFP and presoma (SLP) and the lithium of sulfur doping carbon coating (LiFePO4/silicon) from
The XRD diagram and SEM of sub- battery composite cathode material (SLC) are schemed, it can be seen that Si nano particle and LFP nanometers in composite material
Grain is coated by one layer of amorphous carbon.And the EDS figure (Fig. 7) of composite material shows a small amount of element sulphur doping in the material, is
Caused by sulfur heterocyclic ring monomer 3,4- ethylenedioxy thiophene polymerize with carbonization.
Comparative example 2:
0.2g nano silicon particles, 0.25g 3,4-ethylene dioxythiophene and 0.82g kayexalate are weighed, by its point
It is dispersed in 10ml deionized water, is placed in ball grinder ball milling 2h under inert protective atmosphere and is uniformly mixed.Then, by 0.7g (NH4)2S2O8/6mgFe2(SO4)3It is added in ball grinder, ball milling polymerize 22h under inert protective atmosphere, obtains reaction product.Then,
Reaction product is filtered, filter residue successively uses water and dehydrated alcohol as cleaning solvent, and each washing 3 times obtains presoma and exists
60 DEG C of drying in vacuum drying oven.Presoma is obtained into sulfur doping carbon packet after cooling in 800 DEG C of carbonization 3h under inert protective atmosphere
Cover the lithium ion battery composite cathode active material (abbreviation SC) of silicon.
Comparative example 3:
0.2g LiFePO4,0.25g 3,4-ethylene dioxythiophene and 0.82g kayexalate are weighed, is dispersed
In 10ml deionized water, it is placed in ball grinder ball milling 2h under inert protective atmosphere and is uniformly mixed.Then, by 0.7g (NH4)2S2O8/6mgFe2(SO4)3It is added in ball grinder, ball milling polymerize 22h under inert protective atmosphere, obtains reaction product.Then,
Reaction product is filtered, filter residue successively uses water and dehydrated alcohol as cleaning solvent, and each washing 3 times obtains presoma and exists
60 DEG C of drying in vacuum drying oven.Presoma is obtained into sulfur doping carbon packet after cooling in 800 DEG C of carbonization 3h under inert protective atmosphere
Cover the lithium ion battery composite cathode active material (abbreviation LC) of LiFePO4.
Embodiment 7: carbon coating contains a kind of embodiment of the composite cathode material for lithium ion cell of LiFePO4
The composite anode active material is carbon coating silicon substrate powder silica-base material (Si) and carbon-coated LiFePO 4 for lithium ion batteries (LFP)
The mixture (abbreviation SCLC) of composition, the two ratio are 5:2.The carbon coating silicon substrate powder silica-base material (Si) is comparative example 2
The lithium ion battery composite cathode active material (SC) of obtained sulfur doping carbon coating silicon.The carbon-coated LiFePO 4 for lithium ion batteries (LFP)
For the lithium ion battery composite cathode active material (LC) for the sulfur doping carbon-coated LiFePO 4 for lithium ion batteries that comparative example 3 obtains.
The chemical property that material is prepared in comparative example 2, comparative example 3 and embodiment 6,7 is as shown in Figure 8.SLC and SCLC is negative
Pole keeps specific discharge capacity after good cycle performance, especially 200 circle of SLC cathode circulation to remain to stablize in 0.4A/g
660mAh/g or more, and SC capacity of negative plates only maintains 420mAh/g or so.In addition, Fig. 9 and Figure 10 is to prepare sulphur in embodiment 6
Adulterate the high current density charge and discharge of the lithium ion battery composite cathode active material SLC material of carbon coating (LiFePO4/silicon)
Cycle performance and high rate performance figure.After SLC material recycles 400 times under the conditions of 1,2A/g, capacity it is stable 400mAh/g with
On, coulombic efficiency is up to 99% or more.SLC material capacity under high current density keeps stablizing, and especially holds under the conditions of 10A/g
Amount is maintained at 300mAh/g or so, and when current density is reduced to 0.4A/g, capacity keeps ascendant trend, and it is good to show that material has
Good structural stability.
Embodiment 6 and comparative example 2 compare it is found that relative to pure silicon powder, and the addition of iron phosphate powder substantially increases sulphur
Adulterate the stable circulation of the combination electrode of composite cathode material for lithium ion cell (SLC) composition of carbon coating (LiFePO4/silicon)
Property.
Embodiment 7 and comparative example 2,3 compare it is found that LFP and Si are remixed after carbon coating respectively, significantly as negative electrode material
Improve the cyclical stability of Si cathode.
In short, using excellent cycle stability LFP and Si mixing (first is that LFP and Si material granule mixing after, together together
Shi Jinhang carbon coating, referring to embodiment 6；Second is that LFP and Si are remixed after carbon coating respectively, referring to embodiment 7) after together as
Negative electrode material substantially increases the cyclical stability of Si cathode.
A kind of embodiment 8: embodiment of the composite cathode material for lithium ion cell of carbon coating (LiFePO4/silicon)
0.2g nano silicon particles, 0.08g LiFePO4,1g graphene oxide are weighed, 10ml deionized water is dispersed in
In, it is placed in ball grinder ball milling under inert protective atmosphere and for 24 hours, obtains reaction product.Then, reaction product is filtered, is obtained
Successively use water and dehydrated alcohol as cleaning solvent to filter residue, each washing 3 times dries to obtain presoma for 60 DEG C in vacuum drying oven,
By presoma in 600 DEG C of heat preservation 3h under inert protective atmosphere, obtained after cooling the lithium of the carbon coating (LiFePO4/silicon) from
Sub- battery composite cathode active material.
As shown in figure 11, the present embodiment prepares the coulombic efficiency for the first time of combination electrode half-cell up to 73.3%, cyclic process
In possess apparent charge and discharge platform, and keep stablizing.
A kind of embodiment 9: embodiment of the composite cathode material for lithium ion cell of carbon coating (LiFePO4/silicon)
0.2g nano silicon particles, 0.06g LiFePO4,2g commercial graphite are weighed, is dispersed in 10ml deionized water,
It is placed in ball grinder ball milling 18h under inert protective atmosphere, obtains reaction product.Then, reaction product is filtered, is filtered
Slag successively uses water and dehydrated alcohol as cleaning solvent, and each washing 3 times, 60 DEG C of drying in vacuum drying oven, filter residue is in argon gas guarantor
600-800 DEG C of carbonization had both obtained the lithium ion battery composite cathode activity material of the carbon coating (LiFePO4/silicon) under shield atmosphere
Material.
As shown in figure 12, it is 405mAh/g that the present embodiment, which prepares the specific capacity of reversible discharge for the first time of combination electrode half-cell,
Stablize after circulation 200 in 300mAh/g or more.
A kind of embodiment 10: embodiment of the composite cathode material for lithium ion cell of carbon coating (LiFePO4/silicon)
0.2g nano silicon particles, 0.06g LiFePO4,0.45g aniline are weighed, is dispersed in 10ml deionized water,
Ball milling 2h under inert protective atmosphere is placed in ball grinder to be uniformly mixed.Then, by 0.27g (NH4)2S2O8It is added in ball grinder,
Ball milling polymerize 48h under inert protective atmosphere, obtains reaction product.Then, reaction product is filtered, filter residue successively uses water
With dehydrated alcohol as cleaning solvent, each washing 3 times obtains presoma 60 DEG C of drying in vacuum drying oven.By presoma lazy
Property protective atmosphere under in 700 DEG C of carbonization 3h, the lithium ion battery of the nitrogen-doped carbon cladding (LiFePO4/silicon) is obtained after cooling
Composite anode active material (Si/LFP/C).
Comparative example 4:
0.2g nano silicon particles and 0.45g aniline are weighed, are dispersed in 10ml deionized water, are placed in lazy in ball grinder
Property protective atmosphere under ball milling 2h be uniformly mixed.Then, by 0.27g (NH4)2S2O8It is added in ball grinder, in inert protective atmosphere
Lower ball milling polymerize 48h, obtains reaction product.Then, reaction product is filtered, filter residue successively use water and dehydrated alcohol as
Cleaning solvent, each washing 3 times obtain presoma 60 DEG C of drying in vacuum drying oven.By presoma under inert protective atmosphere in
700 DEG C of carbonization 3h obtain the lithium ion battery composite cathode active material (Si/C) of the nitrogen-doped carbon coated Si after cooling.
Comparative example 5:
0.26g LiFePO4 and 0.45g aniline are weighed, is dispersed in 10ml deionized water, is placed in lazy in ball grinder
Property protective atmosphere under ball milling 2h be uniformly mixed.Then, by 0.27g (NH4)2S2O8It is added in ball grinder, in inert protective atmosphere
Lower ball milling polymerize 48h, obtains reaction product.Then, reaction product is filtered, filter residue successively use water and dehydrated alcohol as
Cleaning solvent, each washing 3 times obtain presoma 60 DEG C of drying in vacuum drying oven.By presoma under inert protective atmosphere in
700 DEG C of carbonization 3h obtain the lithium ion battery composite cathode active material of the nitrogen-doped carbon coated LiFePO 4 for lithium ion batteries after cooling
(LFP/C)。
It as shown in figure 13, is the TG figure of the composite material prepared in embodiment 10, comparative example 4 and comparative example 5, Si in material
With LFP total content 80% or more.It is seen from figure 14 that carbon-coating uniformly wraps in composite material prepared by embodiment 10
Si and LFP particle surface is overlayed on, as can be seen from Figure 15, the first discharge specific capacity of material is up to 3302mAh/g, coulombic efficiency for the first time
It is 66.7%.
A kind of embodiment 11: embodiment of the composite cathode material for lithium ion cell of carbon coating (LiFePO4/silicon)
0.3g nano silicon particles, 0.15g LiFePO4,0.7g aniline are weighed, is dispersed in 10ml deionized water, sets
Ball milling 2h is uniformly mixed under inert protective atmosphere in ball grinder.Then, by 0.45g (NH4)2S2O8It is added in ball grinder,
Ball milling polyase 13 6h, obtains reaction product under inert protective atmosphere.Then, reaction product is filtered, filter residue successively use water and
Anhydrous ether obtains presoma 60 DEG C of drying in vacuum drying oven as cleaning solvent, each washing 3 times.By presoma in inertia
In 600 DEG C of carbonization 5h under protective atmosphere, the lithium ion battery that the nitrogen-doped carbon cladding (LiFePO4/silicon) is obtained after cooling is multiple
Close negative electrode active material.
A kind of embodiment 12: embodiment of the composite cathode material for lithium ion cell of carbon coating (LiFePO4/silicon)
0.3g nano silicon particles, 0.12g LiFePO4,3g glucose are weighed, in deionized water by its ultrasonic disperse, with
Mixed liquor is moved on into hydrothermal reaction kettle afterwards, constant volume about 30ml leads to argon gas protection.It is placed in thermostatical oil bath, 150 under stirring condition
DEG C reaction 6h, obtain reaction product.Then, reaction product is filtered, filter residue successively uses water and dehydrated alcohol as washing
Solvent, each washing 3 times obtain presoma 60 DEG C of drying in vacuum drying oven.By presoma in 800 DEG C under inert protective atmosphere
Be carbonized 3h, obtains the lithium ion battery composite cathode active material of the carbon coating (LiFePO4/silicon) after cooling.
The electrochemical impedance spectrogram that composite material is prepared in the present embodiment is as shown in figure 16.By comparison as can be seen that receiving
Rice silicon (NS), silicon-carbon (SC) and carbon coating (LiFePO4/silicon) (SLC) electrode material impedance are sequentially reduced.Results showed that carbon
The mixing of cladding and LiFePO4 is conducive to improve the electric conductivity and lithium ionic mobility of material.
A kind of embodiment 13: embodiment of the composite cathode material for lithium ion cell of carbon coating (LiFePO4/silicon)
0.2g nano silicon particles, 0.08g LiFePO4,1g polyacrylonitrile (PAN) are weighed, is dispersed in 10ml DMF,
It is placed in ball grinder ball milling under inert protective atmosphere and for 24 hours, obtains reaction product.Then, reaction product is filtered, filter residue according to
Secondary to use water and dehydrated alcohol as cleaning solvent, each washing 3 times dries to obtain presoma for 60 DEG C in vacuum drying oven, by presoma
In 700 DEG C of carbonization 3h under inert protective atmosphere, the lithium ion battery that the carbon coating (LiFePO4/silicon) is obtained after cooling is multiple
Close negative electrode active material.
A kind of embodiment 14: embodiment of the composite cathode material for lithium ion cell of carbon coating (LiFePO4/silicon)
0.3g nano silicon particles, 0.12g LiFePO4,0.8g pyrroles are weighed, is dispersed in 10ml deionized water, sets
Ball milling 2h is uniformly mixed under inert protective atmosphere in ball grinder.Then, by 0.8g FeCl3·6H2O is added in ball grinder,
Ball milling polymerize 46h under inert protective atmosphere, obtains reaction product.Then, reaction product is filtered, filter residue successively uses water
With dehydrated alcohol as cleaning solvent, each washing 3 times obtains presoma 60 DEG C of drying in vacuum drying oven.By presoma lazy
Property protective atmosphere under in 700 DEG C of carbonization 3h, the lithium ion battery of the nitrogen-doped carbon cladding (LiFePO4/silicon) is obtained after cooling
Composite anode active material.
As can be seen from Figure 17, in composite material manufactured in the present embodiment, nano grain surface is coated with one layer of carbon, has
Conducive to the electric conductivity for improving material.As can be seen from Figure 18, the first charge-discharge capacity of composite material is respectively 2435 and 3220mAh/
g。
A kind of embodiment 15: embodiment of the composite cathode material for lithium ion cell of carbon coating (LiFePO4/silicon)
0.2g nano silicon particles, 0.12g LiFePO4,1g pitch are weighed, is dispersed in 10ml toluene, is placed in ball milling
Ball milling is uniformly mixed for 24 hours under inert protective atmosphere in tank.Then, reaction product is filtered, filter residue successively uses water and anhydrous
Ether obtains presoma 60 DEG C of drying in vacuum drying oven as cleaning solvent, each washing 3 times.Presoma is protected in inertia
In 800 DEG C of carbonization 3h under atmosphere, the lithium ion battery composite cathode activity of the carbon coating (LiFePO4/silicon) is obtained after cooling
Material.
A kind of embodiment 16: embodiment of the composite cathode material for lithium ion cell of carbon coating (LiFePO4/lithium titanate)
Weigh 0.6g lithium titanate, 0.24g LiFePO4,0.25g 3,4- ethylenedioxy thiophene and 0.82g polystyrene sulphur
Sour sodium is dispersed in 10ml deionized water, is placed in ball grinder ball milling 2h under inert protective atmosphere and is uniformly mixed.Then,
By 0.7g (NH4)2S2O8/6mg Fe2(SO4)3It is added in ball grinder, the ball milling polyase 13 4h under inert protective atmosphere, obtains anti-
Answer product.Then, reaction product being filtered, filter residue successively uses water and dehydrated alcohol as cleaning solvent, respectively washs 3 times,
Obtain presoma 60 DEG C of drying in vacuum drying oven.Presoma is obtained after cooling under inert protective atmosphere in 800 DEG C of carbonization 2h
To the lithium ion battery composite cathode active material of sulfur doping carbon coating (LiFePO4/lithium titanate).From carbon coating (ferric phosphate
Lithium/lithium titanate) composite material first charge-discharge curve (Figure 19) as can be seen that embodiment 16 prepare lithium ion battery it is compound
Negative electrode active material first charge-discharge curve under the conditions of 0.1C has stabilised platform at 1.55V, remains lithium titanate material
Excellent electrochemical stability, first discharge specific capacity 421mAh/g, coulombic efficiency 91.3%.Lithium prepared by embodiment 16
The discharge capacity of ion battery composite anode active material reaches 305mAh/g, and capacity is stablized in 168mAh/g after circulation 200 times,
First discharge specific capacity 164mAh/g under business LTO 0.5C under equal conditions, capacity is only 98mAh/g (ginseng after recycling 200 times
See Figure 20).The result shows that the present invention can greatly improve the capacity of routine business LTO cathode, and coulombic efficiency and stable circulation
Property is suitable.
Comparative example 6:
Reference implementation example 16, difference is, without LiFePO4, obtains carbon coating lithium titanate.In the material with embodiment 16
Under material test equal conditions, coulombic efficiency is 90.7 to lithium ion battery anode active material prepared by comparative example 6 for the first time, circulation
Specific capacity is only 95mAh/g after 200 times.
Embodiment 16 is compared with comparative example 6 it is found that both present invention increase LFP can improve the specific capacity of LTO, while keep
Excellent cycle stability.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should be managed
Solution, can with modification or equivalent replacement of the technical solution of the present invention are made, without departing from technical solution of the present invention essence and
Range.
Claims (9)
1. the composite anode active material that carbon coating contains LiFePO4, which is characterized in that by LiFePO4 and conventional anode material
Material mixes after carrying out carbon coating, including two kinds of complex methods:
One one step of mixture formed for LiFePO4 and conventional anode material carries out carbon coating simultaneously, obtains carbon coating (phosphoric acid
Iron lithium/conventional anode material) composite cathode material for lithium ion cell；
Two carry out carbon coating respectively for LiFePO4 and conventional anode material after remix to obtain carbon-coated LiFePO 4 for lithium ion batteries and carbon packet
Cover the mixture of conventional anode material, wherein in mixture, the ratio of carbon-coated LiFePO 4 for lithium ion batteries and carbon coating conventional anode material
It is adjustable；
The conventional anode material is selected from any one of silica-base material, lithium titanate.
2. the composite anode active material that carbon coating according to claim 1 contains LiFePO4, which is characterized in that phosphoric acid
One step of mixture of iron lithium and conventional anode material composition carries out carbon coating, the quality of LiFePO4 and conventional anode material simultaneously
Than for 1:100~100:1.
3. the composite anode active material that carbon coating according to claim 2 contains LiFePO4, which is characterized in that phosphoric acid
The mass ratio of iron lithium and conventional anode material is 1:6-3:4.
4. the composite anode active material that carbon coating according to claim 3 contains LiFePO4, which is characterized in that phosphoric acid
The mass ratio of iron lithium and conventional anode material is 2:5.
5. the composite anode active material that carbon coating according to claim 1 or 2 contains LiFePO4, which is characterized in that
The silica-base material is selected from any combination of one or more of silicon powder, the sub- silicon of oxidation, silicon-base alloy, silicon-carbon composite construction.
6. the composite anode active material that carbon coating according to claim 1 or 2 contains LiFePO4, which is characterized in that
The progress carbon coating refers to that active material coats different carbon source presoma, then passes through heat treatment carbonization；The carbon source presoma
Selected from any one of 3,4- ethylenedioxy thiophene, aniline, pyrroles, glucose, pitch, polyacrylonitrile, graphite and graphene.
7. a kind of composite negative plate of lithium ion battery, which is characterized in that include any one of claim 1-6 claim institute
The composite anode active material stated further includes conductive agent and binder.
8. the preparation method of the composite negative plate of lithium ion battery described in claim 7, which comprises the following steps:
Composite anode active material, conductive agent, adhesive dispersions is added, is prepared by grinding or high speed machine stirring uniform
Fluid slurry；By obtained fluid slurry by obtaining lithium ion battery composite cathode piece after being coated with, drying, roll.
9. a kind of lithium ion battery, which is characterized in that the composite negative plate containing lithium ion battery as claimed in claim 7.
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