CN104505493B - A kind of preparation method and application of anode material for lithium-ion batteries - Google Patents
A kind of preparation method and application of anode material for lithium-ion batteries Download PDFInfo
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- CN104505493B CN104505493B CN201410738331.5A CN201410738331A CN104505493B CN 104505493 B CN104505493 B CN 104505493B CN 201410738331 A CN201410738331 A CN 201410738331A CN 104505493 B CN104505493 B CN 104505493B
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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
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- 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
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
This application discloses the preparation method of a kind of anode material for lithium-ion batteries, directly using cheap metal iron powder is raw material, significantly reduces LiFe1‑xMxPO4The production cost of material, technological process is simple, it is not necessary to use the operation equipment of complex and expensive, it is adaptable to industrialized production.The LiFe with carbon coating layer of described preparation1‑ xMxPO4Positive electrode, electrical conductivity is up to 2.0 × 10‑2～6.5 × 10‑1S/cm, has low temp power performance, specific discharge capacity and the high rate performance of excellence.
Description
Technical field
The application relates to the lithium ion battery of this positive electrode of the preparation method and application of positive electrode, belongs to lithium ion
Field of batteries.
Background technology
LiFePO4 (LiFePO4) to have abundant raw material, price as the positive electrode of secondary lithium battery low for material
Honest and clean, environmentally friendly, cycle performance and the feature such as security performance is excellent, be widely used in electric automobile and energy-storage system market.
LiFePO4The native electronic electrical conductivity of material and ion diffusion rates are extremely low, directly results in its specific capacity low with
High rate performance is poor.LiFePO4Having special olivine-type crystal structure, lithium ion can only be along one-dimensional direction during deintercalation
Motion.Therefore, LiFePO4The particle diameter of material determines that lithium ion is at LiFePO4Diffusion path in solid phase.The particle diameter of material is the biggest,
Lithium ion diffusion path in solid phase is the longest, and the removal lithium embedded reaction in electrode is just more difficult to carry out, and the electrode performance of material is the most more
Difference, so the particle diameter reducing material is to improve LiFePO4Lithium ion diffusion rate and then improve the effective means of its electrode performance.
Electrode material necessarily leads to the conductive process of electronics in deintercalate lithium ions reacts, and therefore electrode material must have higher electricity
Electron conductivity.In order to improve LiFePO4Granule is internal has the material of outstanding electric conductivity with intergranular electrical conductivity, generally utilization
Material is to LiFePO4Carry out Surface coating synthesis LiFePO4/ C-material, or utilize metallic element to LiFePO4It is doped process
Synthesis LiFe1-xMxPO4Material.
By optimum synthesis method, preferred carbon source and Simplified flowsheet step, grain size is controlled, carbon-coating is equal to develop one
Even cladding, with low cost and electrochemical performance anode material for lithium-ion batteries have great importance.
Summary of the invention
An aspect according to the application, it is provided that the preparation method of a kind of anode material for lithium-ion batteries, directly uses honest and clean
The metal iron powder of valency is raw material, significantly reduces LiFe1-xMxPO4The production cost of material, technological process is simple, it is not necessary to use
The operation equipment of complex and expensive, it is adaptable to industrialized production.The positive electrode prepared according to herein described method, conductance
Rate is up to 2.0 × 10-2～6.5 × 10-1S/cm, has low temp power performance, specific discharge capacity and the high rate performance of excellence.
The preparation method of described anode material for lithium-ion batteries, it is characterised in that at least comprise the following steps:
A) to containing iron powder, phosphoric acid, weak acid, surfactant system in, add lithium source, carbon source, containing metallic element M
Compound and oxidant, mix homogeneously obtains mixture, and gained mixture is spray-dried obtains presoma；
In presoma, iron powder, phosphoric acid, weak acid, surfactant, lithium source, carbon source, the mol ratio of oxidant are ferrum: phosphoric acid:
Weak acid: surfactant: lithium source: carbon source: containing the compound of metallic element M: oxidant=1～0.9:1:0.05～0.5:
0.1～0.6:1:0.15～1.0:0～0.1:0.2～0.7；
Wherein, the molal quantity in lithium source is in terms of the molal quantity of elemental lithium；The molal quantity of carbon source is in terms of the molal quantity of carbon；Contain
There is the molal quantity of compound of metallic element M in terms of the molal quantity of metallic element M；
B) presoma is placed in dynamic non-active gas, after calcining 4～32 hours at a temperature of 450～950 DEG C, warp
Cool down, crush, obtain described anode material for lithium-ion batteries.
Described anode material for lithium-ion batteries is the LiFe with carbon coating layer1-xMxPO4, 0≤x≤0.10 positive electrode.
Element M strictly occupies LiFePO4Fe position in crystal such that it is able to significantly improve ionic conductivity.Described lithium ion battery is just
The primary particle particle diameter of pole material is 20～80nm, and powder conductivity rate is 2.0 × 10-2～6.5 × 10-1S/cm.Cladding LiFe1- xMxPO4Carbon coating layer thickness be 0.5～15nm, preferably 3～7nm.
Preferably, described metallic element M is selected from Group IIA metal element, Group IIIA metallic element, Group IVB metallic element, VB
At least one in race's metallic element, VIIB race metallic element, group VIII metal element.
Preferably, at least one in Mg, Ti, Nb, V, Mn, Mo, Co, Ni, Al, Zr of described metallic element M.
Preferably, the described compound containing metallic element M is the organic compound containing metallic element M.
Preferably, the median particle diameter of the described iron powder of step a) is 1～950 μm.It is further preferred that the described iron powder of step a)
The median particle size range upper limit selected from 940 μm, 600 μm, 300 μm, lower limit is selected from 100 μm, 150 μm.It is further preferred that
The median particle diameter of the described iron powder of step a) is 50～200 μm.
Preferably, at least one in organic acid of the described weak acid of step a).It is further preferred that described weak acid is selected from
At least one in formic acid, acetic acid, benzoic acid, citric acid, ethanedioic acid, succinic acid, salicylic acid, acetone acid.
Preferably, step a) described weak acid at least two in organic acid.It is further preferred that described weak acid is selected from
At least two in formic acid, acetic acid, benzoic acid, citric acid, ethanedioic acid, succinic acid, salicylic acid, acetone acid.
Preferably, the described surfactant of step a) is selected from polyvinyl pyrrole, glyceryl monostearate, glycerol monolaurate
Ester, dinitrophenyl, sucrose palmitate, sucrose oleate, Polyethylene Glycol, dodecyl-dimethyl amine second lactone, poly-second two
At least one in alcohol octyl phenyl ether, 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG).
Preferably, step a) described lithium source is selected from inorganic lithium salt and/or organic lithium salt.It is further preferred that step a) institute
State at least one in lithium oxalate, lithium carbonate, lithium nitrate, lithium sulfate, Quilonorm (SKB), Lithium hydrate of lithium source.
Preferably, the described carbon source of step a) selected from glucose, sucrose, fructose, maltose, lactose, monocrystal rock sugar, dextrin,
Starch, cellulose, citric acid, ascorbic acid, stearic acid, Polyethylene Glycol, polystyrene, polyvinylpyrrolidone, polyvinyl alcohol
At least one in butyral.
Preferably, at least one in hydrogen peroxide, Ammonium persulfate., sodium chlorate of the described oxidant of step a).
Preferably, the described mixture of step a) is that iron powder, phosphoric acid, weak acid, surfactant, lithium source, carbon source, oxidant exist
The mixture of aqueous phase.Those skilled in the art, can select the suitable water yield according to concrete raw material condition, can obtain uniformly
Scattered system is as the criterion.Preferably, the solid content of the described mixture of step a) is 20%～70%.
Preferably, step a) containing iron powder, phosphoric acid, weak acid, surfactant system by iron powder, phosphoric acid solution, weak acid,
Surfactant mix homogeneously obtains.Preferably, the mass percentage concentration of described phosphoric acid solution is 25%～95%.The most excellent
Selection of land, the mass percentage concentration of described phosphoric acid solution is 60%～85%.
Preferably, at least one in nitrogen, argon, helium of non-active gas described in step b).
Preferably, in step b), the calcination temperature range upper limit is selected from 950 DEG C, 700 DEG C, and lower limit is selected from 450 DEG C, 600 DEG C.
Preferably, calcination time range limit described in step b) be selected from 32 hours, 24 hours, lower limit selected from 5 hours, 10
Hour.Being preferably carried out mode, the preparation method of described anode material for lithium-ion batteries according to the application one, its feature exists
In, at least comprise the following steps:
(1) in reactor, it is sequentially added into metal iron powder and phosphoric acid solution is uniformly mixed, add weak acid mix homogeneously,
Add surfactant mix homogeneously, be separately added into lithium source, carbon source, compound mix homogeneously containing element M, add oxidant
Mix homogeneously, obtains mixture；Gained mixture is spray-dried and prepares precursor；
(2) step (1) gained precursor is placed in dynamic inert atmosphere, is no less than 10h being not less than 700 DEG C of calcinings,
Take out gained solid after being cooled to room temperature and grind, i.e. obtaining the LiFe with cladding carbon-coating1-xMxPO4Positive electrode.
Described anode material for lithium-ion batteries LiFe1-xMxPO4Preparation method, it is characterised in that: described LiFe1- xMxPO4Middle M is one or both or two or more compositions in Mg, Ti, Nb, V, Mn, Mo, Co, Ni, Al, Zr, described
LiFe1-xMxPO4In 0≤x≤0.10.
Another aspect according to the application, it is provided that a kind of lithium ion battery, it is characterised in that described lithium ion battery is just
At least one in the positive electrode that with good grounds any of the above-described method prepares is contained on pole piece.
Preferably, described lithium ion battery is coiled lithium ion battery or stack type lithium ion battery.
Described lithium ion battery contains positive plate, negative plate, isolating membrane, electrolyte or electrolyte, and described positive plate contains
At least one in the positive electrode that any of the above-described method prepares.
The beneficial effect that the application can produce at least includes:
1, the Preparation Method of the positive electrode that the application provides, directly using cheap metal iron powder is raw material, significantly reduces
LiFe1-xMxPO4The production cost of material, technological process is simple, it is not necessary to use the operation equipment of complex and expensive, it is adaptable to industry
Metaplasia is produced.
2, the Preparation Method of the positive electrode that the application provides, it is possible to make doped chemical M strictly occupy Fe position thus significantly carry
High gained LiFe1-xMxPO4The ionic conductivity of material, gained LiFe1-xMxPO4Material electric conductivity is up to 2.0 × 10-2～6.5 ×
10-1S/cm, has the low temp power performance of excellence.
3, the Preparation Method of the positive electrode that the application provides, it is possible to efficiently control LiFe1-xMxPO4The primary particle of material
Particle diameter is to 20～80nm, and to LiFe1-xMxPO4Granule carries out uniform carbon-coating cladding thus significantly improves gained LiFe1-xMxPO4
The ionic conductivity of material, obtained LiFe1-xMxPO4Material has specific discharge capacity and the high rate performance of excellence.
Detailed description of the invention
Below in conjunction with embodiment in detail the present invention is described in detail, but the invention is not limited in these embodiments.
Embodiment 1 sample 1#Preparation
By 0.98mol metal iron powder (median particle diameter D50 is 150 μm) and phosphoric acid solution (phosphoric acid solution of 85wt%, phosphoric acid
Molal quantity be 1mol), be stirred at room temperature uniformly, obtain mixture I.In mixture I add 0.2mol acetic acid and
The citric acid of 0.1mol, stirs, and obtains mixtures II.0.25mol surfactant polyethylene is added in mixtures II
Pyrroles, mix homogeneously obtains mixtures III.Under stirring, (lithium rubs to be sequentially added into 0.5mol lithium carbonate in mixtures III
Your number is 1.0mol), 0.025mol sucrose (carbon molal quantity is 0.3mol), 0.02mol nickel oxalate, mix homogeneously obtains mixture
IV.In mixture IV, add 0.5mol oxidant hydrogen peroxide mix homogeneously, re-use deionized water regulation solid content and obtain
Whole mixture, the solid content of described final mixture is 40%.Mixture is spray-dried and prepares precursor.By gained precursor
Be placed in dynamic nitrogen atmosphere, calcine 10h at 700 DEG C, after being cooled to room temperature, take out gained solid grinding, obtain described lithium from
Sub-positive electrode, is designated as sample 1#。
Embodiment 2 sample 2#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixture I, and the metal iron powder of addition is
1mol；When preparing mixture IV, without nickel oxalate.Other conditions are same as in Example 1, and gained sample is designated as sample 2#。
Embodiment 3 sample 3#Preparation
Concrete steps, proportioning raw materials are same as in Example 1, and difference is: when preparing mixture IV, use
0.02mol magnesium oxalate substitutes 0.02mol nickel oxalate.Other conditions are same as in Example 1, and gained sample is designated as sample 3#。
Embodiment 4 sample 4#Preparation
Concrete steps, proportioning raw materials are same as in Example 1, and difference is: when preparing mixture IV, use
0.02mol butyl titanate substitutes 0.02mol nickel oxalate.Other conditions are same as in Example 1, and gained sample is designated as sample 4#。
Embodiment 5 sample 5#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixture I, and the metal iron powder of addition is
0.94mol；When preparing mixture IV, the molal quantity adding nickel oxalate is 0.06mol.Other conditions are same as in Example 1, gained
Sample is designated as sample 5#。
Embodiment 6 sample 6#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixture I, and the metal iron powder of addition is
0.90mol；When preparing mixture IV, the molal quantity adding nickel oxalate is 0.10mol.Other conditions are same as in Example 1, gained
Sample is designated as sample 6#。
Embodiment 7 sample 7#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixtures II, add the acetic acid of 0.05mol
With the acetic acid of 0.1mol in the succinic acid alternate embodiment 1 of 0.05mol and the citric acid of 0.1mol.Other conditions and embodiment 1
Identical, gained sample is designated as sample 7#。
Embodiment 8 sample 8#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixtures II, add the formic acid of 0.15mol
With the acetic acid of 0.1mol in the salicylic acid alternate embodiment 1 of 0.15mol and the citric acid of 0.1mol.Other conditions and embodiment 1
Identical, gained sample is designated as sample 8#。
Embodiment 9 sample 9#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixtures II, add the acetic acid of 0.2mol
With the acetic acid of 0.1mol in the citric acid alternate embodiment 1 of 0.2mol and the citric acid of 0.1mol.Other conditions and embodiment 1
Identical, gained sample is designated as sample 9#。
Embodiment 10 sample 10#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixtures II, add the acetic acid of 0.4mol
With the acetic acid of 0.1mol in the citric acid alternate embodiment 1 of 0.1mol and the citric acid of 0.1mol.Other conditions and embodiment 1 phase
With, gained sample is designated as sample 10#。
Embodiment 11 sample 11#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixtures III, add 0.25mol dinitro
0.25mol polyvinyl pyrrole in base phenyl alternate embodiment 1.Other conditions are same as in Example 1, and gained sample is designated as sample
11#。
Embodiment 12 sample 12#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixtures III, add the poly-second of 0.25mol
0.25mol polyvinyl pyrrole in glycol octyl phenyl ether alternate embodiment 1.Other conditions are same as in Example 1, and gained sample is remembered
For sample 12#。
Embodiment 13 sample 13#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixtures III, add 0.25mol 12
0.25mol polyvinyl pyrrole in Alkyl Dimethylamine second lactone alternate embodiment 1.Other conditions are same as in Example 1, gained sample
Product are designated as sample 13#。
Embodiment 14 sample 14#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixtures III, add polyvinyl pyrrole
Amount is 0.1mol.Other conditions are same as in Example 1, and gained sample is designated as sample 14#。
Embodiment 15 sample 15#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixtures III, add polyvinyl pyrrole
Amount is 0.4mol.Other conditions are same as in Example 1, and gained sample is designated as sample 15#。
Embodiment 16 sample 16#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixture I, the intermediate value grain of the iron powder of use
Footpath D50 is 10 μm, and when preparing mixtures III, the amount adding polyvinyl pyrrole is 0.6mol.Other conditions and embodiment 1 phase
With, gained sample is designated as sample 16#。
Embodiment 17 sample 17#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixture I, the intermediate value grain of the iron powder of use
Footpath D50 is 600 μm, when preparing mixture IV, adds 0.5mol lithium oxalate and replaces 0.5mol lithium carbonate, and adding carbon molal quantity is
The polystyrene of 0.2mol replaces the sucrose (carbon molal quantity is 0.3mol) of 0.025mol；When preparing final mixture, add
0.2mol Ammonium persulfate. replaces 0.5mol hydrogen peroxide；Sintering process is to sinter 32 hours at 450 DEG C.Other conditions and embodiment
1 is identical, and gained sample is designated as sample 17#。
Embodiment 18 sample 18#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixture I, the intermediate value grain of the iron powder of use
Footpath D50 is 300 μm, when preparing mixture IV, adds 0.5mol Lithium hydrate and replaces 0.5mol lithium carbonate, add carbon molal quantity
Stearic acid for 0.75mol replaces the sucrose (carbon molal quantity is 0.3mol) of 0.025mol；When preparing final mixture, add
0.7mol Ammonium persulfate. replaces 0.5mol hydrogen peroxide；Sintering process is to sinter 5 hours at 950 DEG C.Other conditions and embodiment 1
Identical, gained sample is designated as sample 18#。
Embodiment 19 sample 19#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixture I, the intermediate value grain of the iron powder of use
Footpath D50 is 940 μm, when preparing mixture IV, adds 0.5mol Quilonorm (SKB) and replaces 0.5mol lithium carbonate, and adding carbon molal quantity is
The glucose of 1.0mol replaces the sucrose (carbon molal quantity is 0.3mol) of 0.025mol；Sintering process is to sinter 24 at 600 DEG C
Hour.Other conditions are same as in Example 1, and gained sample is designated as sample 19#。
Comparative example 1 sample D-1#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixtures II, are added without the second of 0.1mol
Acid and the citric acid of 0.1mol.Other conditions are same as in Example 1, and gained sample is designated as sample D-1#。
Comparative example 2 sample D-2#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixtures II, add the acetic acid of 0.2mol
Replace acetic acid and the citric acid of 0.1mol of 0.1mol.Other conditions are same as in Example 1, and gained sample is designated as sample D-2#。
Comparative example 3 sample D-3#Preparation
Concrete steps are same as in Example 1, and difference is: when preparing mixtures III, are added without 0.25mol and gather
Ethylene pyrroles.Other conditions are same as in Example 1, and gained sample is designated as sample D-3#。
Comparative example 4 sample D-4#Preparation
Iron phosphate in molar ratio: lithium carbonate: C=1:1:0.30 is by 1mol iron phosphate, 0.5mol lithium carbonate and 0.025mol
Sucrose adds in ball grinder, adds the zirconium ball of a diameter of 2mm of 80g, with ethanol for solvent ball milling 16h to being fully ground uniformly, and will
Gained mixture is spray-dried and prepares precursor.Gained precursor is placed in dynamic nitrogen atmosphere, calcines 10h at 700 DEG C, cold
But to taking out gained solid after room temperature and grinding, gained sample is designated as sample D-4#。
Embodiment gained sample 1#～19#, comparative example gained sample D-1#～D-4#Preparation condition, proportioning raw materials such as table 1
Shown in.
Embodiment 20 powder sample 1#～19#, the test of D-1#～D-4#
Embodiment gained sample 1#～19#, comparative example gained sample D-1#～D-4#Granularity data exist
Record on MASTERSIZER2000 type laser fineness gage, the results detailed in Table 2.Sample 1#～19#Median particle diameter be 0.55 μ
M～4.31 μm, sample D-1#～D-4#Median particle diameter be 5.11 μm～6.72 μm.
Embodiment gained sample 1#～19#, comparative example gained sample D-1#～D-4#Carbon content data triumphant in Shanghai moral
Record on HCS-140 type high frequency infrared ray carbon sulphur analyser, the results detailed in Table 2.Sample 1#～19#Carbon content be 1.25wt%～
2.87wt%, sample D-1#～D-4#Carbon content be 1.38wt%～1.76wt%.
Embodiment gained sample 1#～19#, comparative example gained sample D-1#～D-4#Specific surface area use nitrogen adsorption methods
NOVA2000e type surface analysis instrument records, the results detailed in Table 2.Sample 1#～19#Specific surface area be 13.24m2/ g～
19.04m2/ g, sample D-1#～D-4#Specific surface area be 11.54m2/ g～14.68m2/g。
Embodiment gained sample 1#～19#, comparative example gained sample D-1#～D-4#PH value data accurate in PHS-3C type
Record on pH meter, the results detailed in Table 2.Sample 1#～19#PH value be 8.4～10.22, sample D-1#～D-4#PH value be
8.64～9.05.
Embodiment gained sample 1#～19#, comparative example gained sample D-1#～D-4#Powder conductivity rate four probe tests
Method records, the results detailed in Table 2 on Four Dimensions 208SI type electric conductivity tester.Sample 1#～19#Powder electricity
Conductance is 1.6 × 10-2S/cm～7.2 × 10-1S/cm, sample D-1#～D-4#Powder conductivity rate be 4.1 × 10-4S/cm～
1.6×10-2S/cm。
The preparation of the full battery of embodiment 21 and test
Respectively with embodiment gained sample 1#～19#, comparative example gained sample D-1#～D-4#As positive active material,
Make full battery, specifically comprise the following steps that
The making of positive plate:
Respectively with embodiment gained sample 1#～19#, comparative example gained sample D-1#～D-4#As positive active material.
By positive active material, binding agent PVDF (Kynoar), conductive black mixing, obtain being uniformly dispersed through high-speed stirred and make
Mixture containing positive active material.In mixture, solid constituent comprises the positive active material of 94wt%, 4wt%
The conductive black of PVDF and 2wt%.Mixture uses NMP (N-Methyl pyrrolidone) to make positive electrode active material chylema as solvent
Material, in slurry, solids content is 75wt%.This slurry is coated in equably aluminium foil two sides, through dry, roll squeezer compacting,
To respectively with embodiment gained sample 1#～19#, comparative example gained sample D-1#～D-4#Positive pole as positive active material
Sheet.
The making of negative plate N1:
Active substance Delanium, binding agent emulsion, thickening agent sodium carboxymethyl cellulose and conductive agent conductive black are mixed
Close, obtain being uniformly dispersed through high-speed stirred and make the mixture containing negative electrode active material.In mixture, solid constituent comprises
The Delanium of 96wt%, the sodium carboxymethyl cellulose of 2wt%, the conductive black of 1wt%, the binding agent of 1wt%.Use water does
Solvent, makes negative electrode active material slurry, and in slurry, solid content is 50wt%.This slurry is coated in Copper Foil two sides, warp equably
Cross dry, roll squeezer compacting, obtain negative plate.
Control the coating weight ratio of positive/negative plate, make capacity of negative plates/positive electrode capacity=1.20.
The making of lithium ion battery:
Respectively with embodiment gained sample 1#～19#, comparative example gained sample D-1#～D-4#As positive active material
Welding conduction lug on positive plate and negative plate, uses the polypropylene, polyethylene composite isolated film of 16um (to be abbreviated as PP/PE multiple
Close isolating membrane) make positive pole and negative pole be sandwiched between and overlapping, wound and formed naked battery core, then encapsulated with aluminum plastic film.Electrolyte
Using the lithium hexafluorophosphate electrolyte solution containing 1M, solvent is for using ethylene carbonate (EC) and dimethyl carbonate (DMC)=3:7 (volume
Than) mixed solvent.Carry out battery after encapsulation being melted into and aging, obtain full battery.
Full battery performance test:
To respectively with embodiment gained sample 1#～19#, comparative example gained sample D-1#～D-4#As positive electrode active material
Matter, the full battery of making carries out performance test, and process is as follows: being respectively placed in by gained battery under 25 DEG C of constant temperatures, temperature is steady
With the constant current charge of 0.5C to 3.65V after Ding, then battery is kept under 3.65V constant-voltage charge, until electric current is down to
0.05C；Discharge into 2.0V with the constant current of 0.5C again, record 25 DEG C of discharge capacities；Subsequently with the constant current charge of 0.5C
To 3.65V, then battery is kept under 3.65V constant-voltage charge, until electric current is down to 0.05C, then battery is placed in-20 DEG C of constant temperature
Condition discharges into 2.0V ,-20 DEG C of discharge capacities of record with the constant current of 0.5C.-20 DEG C of discharge capacity/25 DEG C discharge capacities are i.e.
For cryogenic property, 25 DEG C of effective gross masses of discharge capacity/active substance are 0.5C electric discharge gram volume.
The results detailed in Table 2.
The preparation of embodiment 22 half-cell and test
The making of positive plate:
By gained in embodiment 21 respectively with embodiment gained sample 1#～19#, comparative example gained sample D-1#～D-4#Make
For positive active material, the positive plate obtained cuts into diameter 14mm (S=1.54cm2) positive plate.
The making of negative plate:
With metal lithium sheet as negative electrode.
The making of half-cell:
Barrier film uses the polypropylene isolating membrane (being abbreviated as PP isolating membrane) of 20um, and electrolyte is the carbonic acid with volume ratio 1:1
Vinyl acetate (EC) and dimethyl carbonate (DMC) are solvent, and concentration is 1molL-1LiPF6Solution.
The performance test of half-cell
To respectively with embodiment gained sample 1#～19#, comparative example gained sample D-1#～D-4#As positive electrode active material
Matter, the half-cell of making carries out performance test, and process condition is as follows: at 25 DEG C；The current ratio of specific capacity test is 0.1C；Fill
Discharge voltage range: 2.0～3.8V.
The results detailed in Table 2.
From the data of Tables 1 and 2 it can be seen that
Relatively sample 1#, sample 2#, sample 3#, sample 4#Corresponding data, it can be seen that use different element (Mg, Ti
And any one in Ni) to LiFePO4After being doped process, the gram volume of material slightly fluctuates, but, powder conductivity
Rate significantly improves, and the most corresponding cryogenic property also has clear improvement.
Relatively sample 1#, sample 2#, sample 5#, sample 6#, sample D-4#Corresponding data are it can be seen that along with doping unit
The increase of element Ni content, half-cell gram volume decreases with full battery gram volume, but powder conductivity rate all has with cryogenic property
Significantly improve.When Ni element doping amount is 2mol%, battery shows good capacity and plays and cryogenic property.With
Time, LiFe prepared by heretofore described method1-xMxPO4The LiFePO that material is prepared compared with conventional solid-state method4Material has higher
Powder conductivity rate and more excellent chemical property.
Relatively sample 1#, sample 7#, sample 8#, sample 9#, sample 10#, sample D-1#, sample D-2#Corresponding data can
To find out, material obtained by mixed weak acids solution is used less to use mixed weak acids solution or only use a kind of weak acid solution made
Obtaining material, have higher powder conductivity rate and gram volume, cryogenic property also significantly improves.Use different mixed weak acids solution
The physical-property parameter of material is all had an impact with chemical property, use acetic acid: the mixed weak acids gained material of citric acid=1:1
Material has relatively low specific surface area and a pH value, and higher gram volume and cryogenic property.Addition along with mixed weak acids
Improving, the powder conductivity rate of obtained material is all obviously improved with chemical property, when addition is more than 0.4mol, and electrochemistry
Performance starts slightly to reduce.
Relatively sample 1#, sample 11#, sample 12#, sample 13#, sample 14#, sample 15#, sample 16#, sample D-3#Institute is right
The data answered are it can be seen that to use material obtained by surfactant less to use material obtained by surfactant to have bigger
Specific surface area and less granularity D50, there is higher powder conductivity rate and chemical property simultaneously.Use different
Material obtained by surfactant also shows different physical features and chemical property, when using polyvinyl pyrrole or dinitro
When base phenyl is as surfactant, battery table reveals good cryogenic property and plays with capacity.Along with surfactant adds
The raising of amount, the powder conductivity rate of material all significantly improves with cryogenic property, but when addition is more than 0.4mol, capacity is
Reducing, this amorphous carbon electric conductivity remained after high temperature sintering mainly due to superfluous surfactant is relatively low.
Relatively sample 1#, sample 17#, sample 18#, sample 19#Corresponding data are it can be seen that along with oxidant adds
The raising of amount, the chemical property of material increases, and when using hydrogen peroxide as oxidant, battery table reveals higher gram
Capacity and cryogenic property.Along with the increase of carbon source addition, the residual carbon content of material, specific surface area substantially increase, powder electricity
Conductance is consequently increased, but when the C mole added arrives 1mol, electricity gram volume has declined entirely, for 139.5mAh/g, makes
During with polystyrene or sucrose as carbon source, battery table reveals higher cryogenic property.
The foregoing is only the preferred embodiment of the application, be not limited to the application, for the skill of this area
For art personnel, the application can have various modifications and variations.All within spirit herein and principle, that is made any repaiies
Change, equivalent, improvement etc., within should be included in the protection domain of the application.
Claims (12)
1. the preparation method of an anode material for lithium-ion batteries, it is characterised in that at least comprise the following steps:
A) to containing iron powder, phosphoric acid, weak acid, surfactant system in, add lithium source, carbon source, change containing metallic element M
Compound and oxidant, mix homogeneously obtains mixture, and gained mixture is spray-dried obtains presoma；
In presoma, iron powder, phosphoric acid, weak acid, surfactant, lithium source, carbon source, the compound containing metallic element M, oxidant
Mol ratio be ferrum: phosphoric acid: weak acid: surfactant: lithium source: carbon source: containing the compound of metallic element M: oxidant=1～
0.9:1:0.05～0.5:0.1～0.6:1:0.15～1.0:0～0.1:0.2～0.7；
Wherein, the molal quantity in lithium source is in terms of the molal quantity of elemental lithium；The molal quantity of carbon source is in terms of the molal quantity of carbon；Containing gold
Belong to the molal quantity of compound of element M in terms of the molal quantity of metallic element M；
Surfactant described in step a) is selected from polyvinyl pyrrole, glyceryl monostearate, glyceryl monolaurate, dinitro
Phenyl, sucrose palmitate, sucrose oleate, Polyethylene Glycol, dodecyl-dimethyl amine second lactone, Polyethylene Glycol octyl phenyl
At least one in ether, 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG)；
B) presoma is placed in dynamic non-active gas, after calcining 4～32 hours at a temperature of 450～950 DEG C, through cold
But, crush, obtain described anode material for lithium-ion batteries.
Method the most according to claim 1, it is characterised in that described metallic element M is selected from Group IIA metal element, IIIA
In race's metallic element, Group IVB metallic element, VB race metallic element, VIIB race metallic element, group VIII metal element at least one
Kind.
Method the most according to claim 1, it is characterised in that described metallic element M selected from Mg, Ti, Nb, V, Mn, Mo,
At least one in Co, Ni, Al, Zr.
Method the most according to claim 1, it is characterised in that the median particle diameter of iron powder described in step a) is 1～950 μ
m。
Method the most according to claim 4, it is characterised in that the median particle diameter of iron powder described in step a) is 50～200 μ
m。
Method the most according to claim 1, it is characterised in that weak acid described in step a) is selected from least two in organic acid
Kind.
Method the most according to claim 6, it is characterised in that weak acid described in step a) is selected from formic acid, acetic acid, benzene first
At least two in acid, citric acid, ethanedioic acid, succinic acid, salicylic acid, acetone acid.
Method the most according to claim 1, it is characterised in that lithium source described in step a) is selected from lithium oxalate, lithium carbonate, nitre
At least one in acid lithium, lithium sulfate, Quilonorm (SKB), Lithium hydrate.
Method the most according to claim 1, it is characterised in that carbon source described in step a) is selected from glucose, sucrose, really
Sugar, maltose, lactose, monocrystal rock sugar, dextrin, starch, cellulose, citric acid, ascorbic acid, stearic acid, Polyethylene Glycol, polyphenyl
At least one in ethylene, polyvinylpyrrolidone, polyvinyl butyral resin.
Method the most according to claim 1, it is characterised in that oxidant described in step a) is selected from hydrogen peroxide, persulfuric acid
At least one in ammonium, sodium chlorate.
11. method according to claim 1, it is characterised in that non-active gas described in step b) is selected from nitrogen, argon
At least one in gas, helium.
12. 1 kinds of lithium ion batteries, it is characterised in that containing with good grounds claim 1-11 on the positive plate of described lithium ion battery
At least one in the positive electrode that method described in any one prepares.
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| CN105609764A (en) * | 2015-12-24 | 2016-05-25 | 郑春燕 | High-stability rare earth-lithium iron phosphate composite electrode material |
| CN107910519B (en) * | 2017-11-10 | 2021-02-23 | 华富(江苏)锂电新技术有限公司 | High-capacity and high-cycle-number lithium ion battery |
| CN107845809B (en) * | 2017-11-10 | 2020-11-13 | 江苏华富储能新技术股份有限公司 | Lithium ion battery adopting lithium iron phosphate cathode material and preparation method thereof |
| CN107994230B (en) * | 2017-11-10 | 2021-02-26 | 华富(江苏)锂电新技术有限公司 | Lithium iron phosphate cathode material and preparation method thereof |
| CN109972022B (en) * | 2019-03-26 | 2020-06-12 | 北京石墨烯技术研究院有限公司 | Preparation method of graphene iron-based composite material |
| CN111943281B (en) * | 2020-08-04 | 2022-05-24 | 厦门厦钨新能源材料股份有限公司 | Environment-friendly precursor and composite oxide powder, and preparation method and application thereof |
| CN116097468A (en) * | 2020-09-03 | 2023-05-09 | 宁德时代新能源科技股份有限公司 | Positive electrode material, positive electrode sheet, lithium secondary battery, battery module, battery pack and device |
| CN115472811B (en) * | 2022-10-31 | 2023-06-02 | 宜宾锂宝新材料有限公司 | Positive electrode material precursor, positive electrode material, preparation method of positive electrode material precursor and positive electrode material, and battery |
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