CN107394193A - Anode material for lithium-ion batteries and its preparation method and application - Google Patents
Anode material for lithium-ion batteries and its preparation method and application Download PDFInfo
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- CN107394193A CN107394193A CN201710526766.7A CN201710526766A CN107394193A CN 107394193 A CN107394193 A CN 107394193A CN 201710526766 A CN201710526766 A CN 201710526766A CN 107394193 A CN107394193 A CN 107394193A
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to field of lithium ion battery, and in particular to anode material for lithium-ion batteries and its preparation method and application.The positive electrode chemical formula is LixNiaCobMncRdO2Wherein, R is doped chemical, 0.95 ＜ x ＜, 1.15,0.5 ＜ a ＜ 1.0,0 ＜ b ＜ 0.2,0.0≤c≤0.3, a+b+c=1,0≤d ＜ 0.1；Wherein, nickel element accounts for the mass fraction ＞ 30% of positive electrode.Its preparation method comprises the steps：After raw material including nickel cobalt manganese presoma, Li source compound and macromolecule acids polymers is mixed by metering ratio, re-sinter to obtain the anode material for lithium-ion batteries.The present invention is more beneficial for the bulk phase-doped layer that nickelic lithium ion anode material surface forms stable uniform, improves the security performance of lithium battery.Its preparation method economically feasible, applicability is extensive, positive effect, has preferable application prospect.
Description
Technical field
The present invention relates to technical field of lithium ion, relates generally to field of lithium ion battery anode, and in particular to
Anode material for lithium-ion batteries and its preparation method and application.
Background technology
Recently as smart mobile phone, intelligent automobile, the rise of new-energy automobile, to the power capacity density of mobile device
And the requirement more and more higher of security, anode material for lithium-ion batteries common at present mainly have cobalt acid lithium, LiMn2O4, nickel cobalt manganese
Sour lithium and LiFePO 4.Although wherein cobalt acid lithium energy density is high, because cobalt storage capacity is limited thus is mainly used in 3C fields
Lithium ion battery in, LiMn2O4 and LiFePO 4 material energy density are relatively low, have gradually low containing cobalt by nickle cobalt lithium manganate etc.
The trend that high-nickel material substitutes, nickel cobalt manganese material (abbreviation ternary material) is usually layered rock salt structure material, wherein Ni, Co, Mn
For same cycle adjacent element, aluminium is ionic radius (57 angstroms) and the element that element is close and atomic weight is relatively low such as nickel cobalt manganese, therefore
They can be mixed to form solid solution with arbitrary proportion and keep layer structure constant, have good structural complementarity, preferably
Ground has had both the advantages of cobalt acid lithium, lithium nickelate and LiMn2O4, compensate for respective deficiency, has height ratio capacity, cost is relatively low, follows
Ring stable performance, the features such as security performance is preferable, it is considered as the choosing of the ideal of anode material for lithium-ion batteries of future generation.
Research shows, it is more harsh to prepare requirement of rising of the nickel-cobalt lithium manganate material with nickel content to sintering condition,
Usual nickel content is higher, and the moisture and atmosphere of production environment are extremely important, and it mainly influence to be occurred during fruit is sintered
The dislocation mixing of nickel/elemental lithium, and then the capacity for influenceing positive electrode plays and efficiency first.The nickel content of other material is got over
Height, the variation of valence of nickel is larger in charge and discharge process, Ni2+, Ni3+, Ni4+Can exist, in lithium battery, such as material granule
It is directly exposed in electrolyte, the high price nickel ion Ni of material surface4+(solid-state is organic for the SEI films that meeting oxidation material surface is formed
Dielectric film) and electrolyte organic molecule, and then weaken lithium battery circulation and security performance, influence lithium ion battery
Using.
Usual positive electrode is prepared as high-temperature physics diffusion process, and positive pole presoma is will be present in by high temperature and atmosphere
Progressively diffusion mobility is into macro-scale presoma body phase with plasma state for the oxidate for lithium on surface, while under oxygen atmosphere
Generation with certain crystallographic structure can intercalation materials of li ions, due to a kind of superficial layer lithium also particulate matter, in diffusion process
The contact area and skewness of lithium source and predecessor are possible to that the uneven of local lithium source can be formed.Equally carrying out surface
During being mixed with doped chemical to permeate/be diffused into material surface there is also it is identical the problem of, for this need try to solve
The distribution and diffusion problem on persursor material surface such as lithium source, dopant.Phase has been proposed in many open and patent documents
The method answered and application.
The problem of another aspect is present is that positive electrode is prepared generally by containing the crystallization water (such as monohydrate lithium hydroxide)
And constitution water (such as nickel cobalt manganese/aluminium hydroxide, monohydrate lithium hydroxide) etc., and contain carbonate (such as lithium carbonate and doping bag
Cover and use carbonate) etc., above-mentioned Light ends are decomposable asymmetric choice net (within 500 DEG C) in relatively low temperature actually in later stage preparation process
Weightlessness, from the aspect of sintering angle and labor intensity, it is actually and uneconomical that above-mentioned Light ends are sloughed using high temperature sintering.For
This needs to prepare the new synthesis/preparation method of angle exploration from material, if reactant tentatively to be mixed to expansion using physical means
Dissipate more preferably.
Chinese patent CN201510194106.4 discloses the method that two-step method prepares anode material for lithium-ion batteries.Will system
Standby obtained nickel cobalt aluminium hydroxide Ni0.80Co0.15Al0.05(OH)2Powder 300 DEG C/3~4h in atmosphere, naturally cools to room
Temperature, obtains bar-shaped cobalt nickel oxide aluminium, then gained cobalt nickel oxide aluminium, lithium source and citric acid are soluble in water, are stirred at room temperature to obtain
Suspension, this suspension is obtained into gel in 80~90 DEG C of stirring in water bath；It is dried rear grind into powder；Powder is placed again
750 DEG C/2~4h in atmosphere, naturally cools to room temperature, produces LiNi0.80Co0.15Al0.05O2。
Chinese patent CN201410004698.4 discloses lithium nickel cobalt aluminum oxide composite positive pole, its method prepared
And lithium ion battery.Composite positive pole is in core/shell structure, and wherein kernel is the mixed solution carrying out washing treatment through alcohol and organic acid
LiNi1-x-yCoxAlyO2(0 ＜ x≤0.2,0 ＜ y≤0.1), shell is metal oxide layer.First by nickel cobalt aluminium complex and lithium
Source compound in molar ratio 1：(0.95~1.15) uniformly mixed using ball milling mixing, three-dimensional hybrid or VC mixers, then with 2-
10 DEG C/min is warming up to 750~850 DEG C and is passed through air either oxygen roasting, then through natural cooling, crushing, classification, screening institute
State matrix material and obtain matrix material, then use C1-C6Fatty alcohol and C1-C6The mixed solution of organic acid is to described matrix material (base
The mass ratio of body material and the alcohol and the mixed solution of organic acid is (1~12):4, have in the mixed solution of alcohol and organic acid
The mass ratio of machine acid and alcohol is (1~38):19) carry out 2-8 washing and obtain inner nuclear material；The inner nuclear material is added into gold again
Belong to salt (aluminum nitrate, magnesium nitrate, butyl titanate, zirconium nitrate, ammonium metavanadate, tetraethyl orthosilicate, zinc acetate, copper nitrate, lanthanum nitrate,
1 kind or at least two kinds of of combination in cerous nitrate and nitric acid tin, metal salt are 0.1~15wt% of the inner nuclear material quality) it is molten
Suspension is made in liquid, spray drying, anneals and the lithium nickel cobalt aluminum oxide composite positive pole of core/shell structure is made.
Patent CN201410482634.5 discloses the preparation method of spherical nickel-cobalt mangaic acid lithium.Persursor material carries out solid-liquid
Separation, is cleaned with pure water, is then dried in 45 DEG C/6h, is obtained the mixed carbonate of spherical nickel cobalt manganese；The mixing carbon that will be obtained again
Hydrochlorate carry out the pre-heat treatment (6 DEG C/min rises to 480 DEG C/8h and obtains oxide, take the lithium hydroxide of metering with pure water in mass ratio
1:1.8 mixing, the ball milling 2h in ball mill, the oxidation of precursor thing after lithium salts slurry and preheated processing is made in molar ratio
Li:(Ni+Co+Mn)=1.3:2 are stirred mixing 40min；The product of gained is heat-treated (with 3 DEG C/min liter again
Warm speed rises to 480 DEG C from room temperature, is incubated 4h, then rises to 850 DEG C/15h with 3 DEG C/min heating rate), and through naturally cold
But, spherical nickel-cobalt mangaic acid lithium is obtained.
Patent CN201410468655.1 discloses the production method of nickel-cobalt lithium manganate material.Nickle cobalt lithium manganate will be burnt till
Material and nano-grade aluminum hydroxide, and boric acid is added, 10min is stirred in high speed mixer high speed, is well mixed material；Will
Well mixed material is heated to 700 DEG C in rotary kiln.720 DEG C are heated in rotary kiln；The nickel that would be heated to after 720 DEG C
Cobalt lithium manganate material is encased in pressure-resistant hold-up tank；Tank is covered and be sealed and stored, pure oxygen is passed through from air inlet to hold-up tank, until
Air pressure reaches 2~4atm and stops being passed through pure oxygen in hold-up tank；Roll more than hold-up tank 5h, hold-up tank is stood, to nickel cobalt mangaic acid
Lithium material carries out Temperature fall；After nickel-cobalt lithium manganate material is cooled into normal temperature, the air pressure of hold-up tank is discharged, opens hold-up tank,
Take out nickel-cobalt lithium manganate material；Nickel-cobalt lithium manganate material is put into high speed dispersor after taking-up, is divided by high speed dispersor
Dissipate and screening is packed.
Patent CN201310693296.5 discloses the preparation method of high-voltage lithium-battery cathode material nickle cobalt lithium manganate.Hydrogen
Cobalt nickel oxide manganses and lithium salts press Li:(Ni+Co+Mn)=(1.05-1.10):1 mol ratio adds ball milling 2-6h in ball grinder, makes
It is well mixed；Above-mentioned mix products are fitted into crucible to be put into sintering furnace, are warming up to 900-1100 DEG C/6-24h, cooling, powder
After broken, monocrystalline or class monocrystalline nickle cobalt lithium manganate are obtained；By Mg:Zr=x:3-x mol ratio, wherein 1≤x≤2, by magnesium acetate and
Acetic acid zirconium is added in deionized water, is configured to total metal ion 2-5mol/L mixed solution and by (Mg+Zr):(Ni+Co+Mn)
=0.002-0.006 mol ratio is added in the aqueous phase system of monocrystalline or class monocrystalline nickle cobalt lithium manganate, stirring 0.5-2.0h, then
Dynamically dried at 100-150 DEG C, then by drying object in 400-700 DEG C/4-8h, you can obtain coated with uniform Mg and Zr height
Voltage lithium cells anode material nickel cobalt manganic acid lithium product.
Patent CN201610253176.7 and CN201610253178.6 disclose stratiform nickel-cobalt lithium manganate cathode material
Preparation method.Will be stoichiometrically by solid-state Mn (NO3)2、CoCO3、Ni(NO3)2·6H2O and Li2CO3Mixture input rotation
In the drum cavity turned；Mixture is thrown away put into the drum cavity again under the action of the centrifugal force by the roller of rotation from inner chamber
In, obtain well mixed mixture；Dispersant is added into above-mentioned well mixed mixture again and carries out ball milling；Then by ball
Slurry after mill is placed in drying box and dried, and obtains presoma；Presoma is subjected to pre-burning in resistance furnace；Ground after pre-burning
Mill, then the material after grinding is placed in swinging roaster/resistance furnace and is calcined.The present invention is made using centrifugal force and ball-milling technology
The material that must be mixed realizes random shuttling movement, so as to reach the batch mixing uniformly purpose without dead angle；Pass through pre-burning and roasting again
Obtain the nickel-cobalt lithium manganate cathode material of excellent electrochemical performance.
The content of the invention
Present invention solves the technical problem that it is：Existing nickelic anode material for lithium ion battery needs in use
Its structural stability is improved, because the diffusion inequality of lithium causes free lithium content high, conventional simple doping method causes doping member
Element is uneven and is difficult to reach ideal effect；And the demands such as normal sintering process energy consumption height are used in process of production, therefore
Urgently develop a kind of process of new simple possible.
In order to solve the above technical problems, it is of the invention after nickelic positive electrode preparation technology is analyzed, and to presoma thing
The hole that fractograph analysis (Fig. 1) finds some macro-scales in presoma thing structure to be present is carried out, reactant feed is in certain bar
Possess the possibility permeated into predecessor body under part, thus creative pass through the not volatile high temperature decomposable asymmetric choice net of additional normal temperature
The poly- polyacid of high-purity (macromolecule acids polymers) lithium source and doped chemical are become into soluble element step by step, sintering
Lithium source before, doped chemical and poly- polyacid etc. are partly diffused into presoma body, in a heated condition poly- polyacid and its salt
Different metallic elements can be still redissolved and is distributed after exploded, ultimately generate the homogeneous lithium of external and internal compositionses lithium
Ion battery positive electrode, it is possible to reduce one of high temperature sintering process, while to lifting the chemical property of nickelic positive electrode
There is larger lifting.
The present invention further forms slurry using in material dispensing preparatory phase addition deionized water simultaneously, or uses
Dry process is into powder, it is possible to achieve comprehensive compatibility of material preparation section, i.e., without transforming existing equipment
The production of nickelic positive electrode either can be conveniently realized under replacement state.
The present invention another discovery is that high-purity poly- polyacid is a kind of weak acid, it has certain molecular weight, at normal temperatures
Not volatile pollution environment, it can completely decompose again at high temperature, will not have obvious influence to the component of existing presoma, i.e.,
It is the local formation for having an impact, also promoting doped chemical participation positive electrode crystal structure in follow-up sintering synthesis, most
End form into uniform thin layer doped layer, so as to reduce during the use of positive electrode later stage directly with the electrolyte of reproducibility into
Part contact, reach lifting lithium ion battery safety and the purpose of cycle performance.
Specifically, in view of the shortcomings of the prior art, the invention provides following technical scheme：
A kind of anode material for lithium-ion batteries, it is characterised in that chemical formula LixNiaCobMncRdO2Wherein, R is doping
Element, 0.95 ＜ x ＜, 1.15,0.5 ＜ a ＜ 1.0,0 ＜ b ＜ 0.2,0.0≤c≤0.3, a+b+c=1,0≤d ＜ 0.1；Wherein,
The nickel element accounts for the mass fraction ＞ 30% of positive electrode, preferably ＞ 40%, it is furthermore preferred that being ＞ 45%.
Preferably, in above-mentioned positive electrode, the mass fraction that the free lithium of the positive electrode accounts for positive electrode is more than 0,
It is less than 0.5% less than 1%, preferably greater than 0, it is furthermore preferred that to be less than 0.2% more than 0.
Preferably, in above-mentioned positive electrode, the free lithium mass fraction is more than 0, less than 0.1%, more there is choosing, is
More than 0, less than 0.05%.
Preferably, the lithium hydroxide that dissociates in above-mentioned positive electrode, in the positive electrode accounts for the mass fraction of positive electrode
It is less than 0.3% more than 0, preferably greater than 0 is less than 0.1%, it is furthermore preferred that to be less than 0.05% more than 0.
Preferably, in above-mentioned positive electrode, the mass fraction that the free carbonic acid lithium of the positive electrode accounts for positive electrode is big
It is less than 1% in 0, preferably greater than 0 is less than 0.5%, it is furthermore preferred that to be less than 0.2% more than 0.
Preferably, in above-mentioned positive electrode, the pH value of the positive electrode is 11-11.7.
Preferably, in above-mentioned positive electrode, the positive electrode average grain diameter (Dv50) it is 2.0-16 μm, specific surface area is
0.2-1.2m2/g。
The present invention also provides the preparation method of above-mentioned anode material for lithium-ion batteries, it is characterised in that comprises the steps：
By the raw material including presoma, Li source compound, doping element compound and macromolecule acids polymers by metering
After mixing, the anode material for lithium-ion batteries is obtained through oversintering；
Wherein, the presoma chemical formula is NiaCobMncRd(OH)2, wherein, R is doped chemical, 0.5 ＜ a ＜ 1.0,0
＜ b ＜ 0.2,0.0≤c≤0.3, a+b+c=1,0≤d ＜ 0.1；The positive electrode chemical formula is LixNiaCobMncRdO2Its
In, 0.95 ＜ x ＜ 1.15, nickel element accounts for the mass fraction ＞ 30% of positive electrode, preferably ＞ 40%；
The macromolecule acids polymers contain acidic-group；Relative molecular mass is 3000-4000000.
Preferably, in above-mentioned preparation method, the macromolecule acids polymers account for the quality point of raw material based on effective ingredient
Number is 0.1-10%.
Preferably, in above-mentioned preparation method, in the macromolecule acids polymers, acidic-group accounts for polymer acid Type of Collective
The mass fraction of thing is 23%-63%.
Preferably, in above-mentioned preparation method, the macromolecule acids polymers are selected from acrylic polymer, the propylene
Acids polymers are selected from polyacrylic acid, styrene acrylic based polyalcohol or polystyrene-based glucosyl group acrylate copolymer
One or more, preferably acrylic acid polymer and/or polystyrene-based glucosyl group acrylate copolymer.
Preferably, the process crushed is also included in above-mentioned preparation method, after the roasting process.
Preferably, in above-mentioned preparation method, one kind in aluminium, magnesium, zirconium, titanium, tungsten, lanthanum or yttrium of the doped chemical or
It is two or more.
Preferably, in above-mentioned preparation method, the Li source compound is selected from containing lithium hydroxide, lithium oxalate, lithium carbonate, nitric acid
It is more than one or both of lithium, lithium acetate, lithium fluoride, lithium chloride, tert-butyl alcohol lithium or lithium citrate.
Preferably, in above-mentioned preparation method, as d ≠ 0, the raw material also includes the compound containing doped chemical, described
Compound is selected from oxide, salt or hydroxide, average grain diameter (Dv50) it is 0.02-3 μm.
Preferably, in above-mentioned preparation method, the raw material also includes water, and the mass fraction that water accounts for raw material is 0-30wt%.
Preferably, in above-mentioned preparation method, the sintering temperature is 700-880 DEG C, and sintering atmosphere is oxygen-enriched air, oxygen
Volume content is 50-70%, and roasting time is 5-10 hours.
Preferably, in above-mentioned preparation method, for add water raw material preparation mixture, the roasting process it
Before, include the process of pre-burning, the burn-in process comprises the steps：
At 200-500 DEG C, under conditions of oxygen volume is 40%-65%, 5-20 hours are sintered.
Preferably, in above-mentioned preparation method, the mixed process comprises the steps：
After raw material high-speed stirred 1-2 hours, then stirring at low speed 0.2-6h；Wherein, the speed of high-speed stirred is 20-
40rmp, the speed of stirring at low speed is 3-10rmp, and corresponding stirring vane edge linear velocity is 7.5-150m/min.
The present invention also provides a kind of anode material for lithium-ion batteries, it is characterised in that is prepared by above-mentioned preparation method.
The present invention also provides a kind of lithium ion battery, it is characterised in that includes above-mentioned positive electrode.
The present invention also provides the application of above-mentioned positive electrode or above-mentioned lithium ion battery in lithium electric energy source domain.
It is an advantage of the invention that：The present invention is immersed in type using the auxiliary generation of poly- polyacid family macromolecule compound is uniform
Reactant, high-purity poly- polyacid can thermally decompose completely in later stage sintering process, while be more beneficial for nickelic lithium ion anode material
Expect that surface forms the bulk phase-doped layer of stable uniform, be advantageous to avoid positive electrode powder granule during later stage use direct
Contacted with electrolyte, so as to be advantageous to use of the nickelic positive electrode in high voltage, long circulating system, while improve lithium electricity
The security performance in pond.This method economically feasible, applicability is extensive, positive effect, has preferable application prospect.
Brief description of the drawings
Fig. 1 is nickelic forerunner's body section electron microscope (Cross-section SEM), multiplication factor described in embodiment 3
For 3000 times.
Fig. 2-a, Fig. 2-b, Fig. 2-c are respectively embodiment 4, comparative example 1, the ESEM of positive electrode described in comparative example 2
Figure, 10000 times of multiplication factor.
Fig. 3 is the 1C/1C circulation volume conservation rate figures of embodiment 3, embodiment 4 and comparative example 2 at 60 DEG C.
Fig. 4-a are the nail thorn result of the test of embodiment 1.
Fig. 4-b are the nail thorn result of the test of comparative example 1.
Embodiment
In view of lithium diffusion is uneven in anode material for lithium-ion batteries at present, the lithium content that dissociates is high, causes cathode material structure
Less stable, lithium ion battery gas production big the problems such as limiting its application field of preparation, the present invention provide one kind and prepare height
The method of nickel lithium ion anode material, by adding high-purity poly- polyacid in dispensing stage, poly- polyacid is decomposed in advance in sintering process,
Doped chemical and presoma generate the homogeneous doping type nickel cobalt manganese anode material of body phase with lithium salts reaction, are advantageous to lift positive pole material
The physics and chemical property of material, expand the application field of the positive electrode.The technique is prepared simply, can combine doping process
It is good that uniformity is prepared together, and crystal structure is complete, and dissociate the low material of lithium content, is advantageous to prepared by high ni-type positive electrode
The raising of lithium battery chemical property, expand the business application of lithium ion battery.
In a kind of preferred embodiment, the present invention provides a kind of Uniform Doped type nickelic lithium ion anode material of preparing
Method, will in dispensing stage by adding high-purity poly- polyacid (that is, macromolecule acids polymers) and its solution in dispensing stage
The molten liquid with dilution of doped chemical gathers more acid reactions/dissolving immersion and is diffused into persursor material body, improves doped chemical
With the dispersive property of bulk material, the not volatile poly- polyacid of sustained release meeting in pyrolysis process during later stage sintering fruit
Lasting play helps diffusion, and poly- polyacid is decomposed completely during oxidation and sinter atmosphere, ultimately form target product lithium from
Sub- cell positive material.
Wherein, above-mentioned poly- polyacid and its solution are the high molecular polymers for containing more carboxyl/acid group on molecule chain,
There is the function of Bronsted acid under normal temperature and hot conditions, it is typical such as Lubrizol Corp. of U.S. production K702 high molecule multifunctions third
Olefin(e) acid polymer solution.
Wherein, above-mentioned poly- polyacid, it can be added using wet together with presoma, lithium salts, doped chemical thing, deionized water
Method technique batch mixing, can also be with presoma, and lithium salts, doped chemical thing together prepare by dry process batch mixing.
Preferably, above-mentioned poly- polyacid, its addition are 0.1-10wt% by substance content.
Preferably, in above-mentioned doping process, wherein lithium salts is lithium carbonate, lithium oxalate, monohydrate lithium hydroxide, lithium acetate, fluorine
Change the one or more of lithium etc., purity is technical grade either LITHIUM BATTERY, described target dopant be magnesium, titanium, aluminium, yttrium, zirconium,
Lanthanum, tungsten etc. have an oxide of certain particle size, and salt is a kind of or several in oxygen oxide.
Preferably, in the nickelic lithium ion anode material of above-mentioned doping, described high-nickel material refer in structural formula nickel content by
The positive electrode of mole meter >=0.6, or nickel element content ＞ 30% positive electrode by mass, its presoma is before commercially available
Body is driven, is typically NMC622 (molecular formula Ni0.6Co0.19Mn0.21(OH)2), NMC71515 (molecular formula Ni0.69Co0.14Mn0.16
(OH)2), NMC811 (molecular formula Ni0.81Co0.10Mn0.11(OH)2), NCA (molecular formula Ni0.82Co0.17Al0.01(OH)2), NMC955
(molecular formula Ni0.90Co0.03Mn0.07(OH)2) etc. hydroxide, oxide and other compositions.
Presoma particle diameter D of the present inventionV50For 5-10 μm.
Nickel content detects to obtain by ICP described in positive electrode of the present invention.
Preferably, above-mentioned wet method preparation process comprises the following steps.
A) dispensing.First presoma is weighed and is added in dispersing apparatus, adulterates a kind of or several raw material of object
It is added in poly- more acid solutions and is dispersed with stirring, then by lithium salts, deionized water is added to preliminary scattered equal in foregoing poly- more acid solutions
Even formation slurry, is finally added slurry into presoma powder under agitation, and it is qualified to continue to be dispersed to by technological requirement
Stock discharge.
B) it is pre-sintered.Slurry is fitted into container to be put into Muffle furnace and is warming up to 200-500 DEG C with 5-15 DEG C/min, is passed through
Oxygen-enriched air is not passed through gas, insulation 60~150min dischargings either.
C) sinter.Material b) prepared is encased in ceramic alms bowl, then material is put into sintering in sintering furnace and obtained.
D) crush.Above-mentioned material is crushed using pulverizer, that is, obtains thing of the present invention.
Preferably, above-mentioned dry preparation process comprises the following steps：
A) dispensing.First presoma is weighed and is added in dispersing apparatus, then will gather in more acid solutions and add under agitation
Enter and be uniformly dispersed into dispersing apparatus, then a kind of or several raw material of object will be adulterated under agitation, and lithium
Salt, which is added in dispersion machine, to be uniformly dispersed to form dry material discharging.
B) sinter.Material a) prepared is encased in ceramic alms bowl, then material is put into sintering in sintering furnace and obtained.
D) crush.Above-mentioned material is crushed using pulverizer, that is, obtains thing of the present invention.
The chemical formula of anode material for lithium-ion batteries of the present invention is LixNiaCobMncRdO2, wherein, R is doping member
Element, 0.95 ＜ x ＜, 1.15,0.5 ＜ a ＜ 1.0,0 ＜ b ＜ 0.2,0.00≤c≤0.3, a+b+c=1,0≤d ＜ 0.1.
Preferably, 1.0≤x≤1.07.Preferably, 0.6≤a≤0.95.Preferably, 0.05≤b≤0.19.Preferably, 0
≤c≤0.21.Preferably, 0≤d≤0.09.
The present invention uses the polycarboxylic acids of high-purity, and it is mainly in before sintering to lithium salts and presoma " corrosion ", production
Thing carries out once phase counterdiffusion in porous material in advance, and its salt generated still can conduct after the decomposition of later stage organic matter
Synthetic continues reaction in-situ.The polyacrylic acid alkali salt used in the prior art mainly plays dispersant use, for improving
The inhomogeneities of material, but the sodium potassium calcium wherein used is the impurity that can destroy positive electrode stratiform structure, generally in material
Middle content requirement is more low better within 10ppm, different from the present invention.
The monomer of acrylic polymer of the present invention includes acrylics or methacrylic acid lipid, or also wraps
Including other alkenes has the acrylic acid either methacrylic acid monomer of substitution structure.For example, contain styryl and/or contain
The monomer of glucose structure etc..
The present invention also provides nickelic lithium ion anode material in manufacture lithium rechargeable battery, portable storage device and storage
Application in energy power station.
The present invention also provides a kind of lithium rechargeable battery, it is characterised in that is used comprising above-mentioned nickelic lithium ion battery
Positive pole made of positive electrode.
The present invention also provides a kind of lithium rechargeable battery, it is characterised in that the nickelic lithium ion anode material is logical
Above-mentioned method is crossed to be prepared.
Illustrate positive electrode of the present invention and its preparation method and application below by specific embodiment.
Used each reagent and instrument source are as shown in table 1 and table 2 in example below.
Agents useful for same information in the embodiment of the present invention of table 1
Device therefor information in the embodiment of the present invention of table 2
Embodiment 1
Machine is merged from 1000L, opens stirring (500rpm), adds 381.3kg nickel cobalt manganese forerunner under agitation
Body (Ni0.81Co0.10Mn0.11(OH)2, then weigh 156.6kg carbonic acid powder for lithium and be added in fusion machine, press under agitation
80wt% solid contents add 222.3kg deionized waters, the polystyrene-based glucosyl group acrylate copolymers of 1.1kg, after stirring 2h
Further reduce speed (50rpm) stirring 20min and discharge that to form the plaster material with certain forming degree standby.
Using ventilation 24m roller kilns.It is 200 DEG C to set heating zone temperature, and being passed through oxygen-enriched air, (oxygen content volume ratio is
45%, gas input 400m3/ h) under the conditions of above-mentioned plaster material be encased in ceramic alms bowl carry out first sintering, sinter
Time is 15h, and material air-isolation is cooled into normal temperature, weighs the weight of disengaging material, counts burn tinctuer (first sintering powder
Expect the ratio of poor quality with powder quality before first sintering) it is 27.6%.Then crushed with cyclone vortex pulverizer, powder
Humidity≤2% of surrounding air is controlled when broken, obtains first sintering semi-finished product.
Using ventilation 24m roller kilns.It is 700 DEG C to set heating zone temperature, is passed through (oxygen content volume under the conditions of oxygen-enriched air
Than for 70%, gas input 600m3/ h) above-mentioned first sintering semi-finished product powder is encased in ceramic alms bowl be sintered,
Sintering time is 8h, and material air-isolation is cooled into normal temperature, weighs the weight of disengaging material, statistics burn tinctuer (second of burning
Tie the ratio of powder quality before powder quality difference sinters with second) it is 2.1%.Then powder is carried out with cyclone vortex pulverizer
It is broken, obtain nickel-cobalt lithium manganate cathode material, the granularity (D of materialv50) it is 2.0 μm, specific surface area 1.2m2/g。
It is as shown in table 3 to result after the quantitative elementary analysis of positive electrode with ICP：
Positive electrode element characterization result described in the embodiment 1 of table 3
| Element | Li | Co | Ni | Mn | Al | Ca | Mg |
| Mass ratio | 7.25 | 5.97 | 48.49 | 5.27 | 0.0198 | 0.0020 | 0.0024 |
| Atomic weight | 6.94 | 58.93 | 58.69 | 54.94 | 26.98 | 40.00 | 24.00 |
| Molal quantity | 1.04 | 0.10 | 0.82 | 0.096 | 0.0007 | 0.00005 | 0.00010 |
| Element | Na | P | S | Ti | Y | Zn | Zr |
| Mass ratio | 0.0037 | 0.0047 | 0.0547 | 0.0398 | 0.0210 | 0.0000 | 0.0023 |
| Atomic weight | 23.00 | 30.97 | 32.00 | 40.00 | 88.91 | 65.41 | 91.22 |
| Molal quantity | 0.00016 | 0.00015 | 0.00171 | 0.0001 | 0.0002 | 0.00000 | 0.00003 |
Embodiment 2
From 1000L plough batch mixers, stirring (20rpm) is opened, before adding 380.5kg nickel cobalt aluminium under agitation
Drive body (Ni0.82Co0.17Al0.01(OH)2, then weigh 285.6kg acetic acid powder for lithium and be added in plough batch mixer, in stirring state
Lower addition 66.62kg C934 resins, 226.1kg deionized waters, 1.26kg lanthanum nitrate hexahydrates (technical grade, the content of purity 98.5%
Lanthanum content is about 1000ppm in terms of finished product), (technical grade, W content is about in terms of finished product for the content of purity 97.5% for 0.27kg ethanol tungsten
For 300ppm), further speed (3-5rpm) the stirring 6h that reduces discharges to form the paste with certain forming degree after stirring 2h
Expect standby.
Using ventilation 24m roller kilns.It is 500 DEG C to set heating zone temperature, and being passed through oxygen-enriched air, (oxygen content volume ratio is
65%, gas input 400m3/ h) under the conditions of above-mentioned plaster material be encased in ceramic alms bowl carry out first sintering, sinter
Time is 16h, and material air-isolation is cooled into normal temperature, weighs the weight of disengaging material, and statistics burn tinctuer is 25.3%.Then
Crushed with cyclone vortex pulverizer, humidity≤2% of surrounding air is controlled during crushing, obtains first sintering semi-finished product.
Using ventilation 24m roller kilns.It is 880 DEG C to set heating zone temperature, is passed through (oxygen content volume under the conditions of oxygen-enriched air
Than for 70%, gas input 600m3/ h) above-mentioned first sintering semi-finished product powder is encased in ceramic alms bowl be sintered,
Sintering time is 8h, and material air-isolation is cooled into normal temperature, weighs the weight of disengaging material, and statistics burn tinctuer is 5.1%.So
Crushed afterwards with cyclone vortex pulverizer, obtain nickel-cobalt lithium manganate cathode material, the granularity (D of materialv50) it is 8.5 μm, compare table
Area is 0.53m2/g。
Embodiment 3
From 1000L kneaders, stirring (30rpm) is opened, adds 379.3kg nickel cobalt manganese presoma under agitation
(Ni0.90Co0.03Mn0.07(OH)2, then weigh 114.4kg fluorination powder for lithium and be added in kneader, add under agitation
2.48kg C940 resins, further speed (10rpm) the stirring 30min that reduces discharges to be formed with certain forming degree after stirring 1h
Plaster material it is standby.
Using ventilation 24m roller kilns.It is 750 DEG C to set heating zone temperature, is passed through (oxygen content volume under the conditions of oxygen-enriched air
Than for 70%, gas input 600m3/ h) above-mentioned plaster material is encased in ceramic alms bowl be sintered, sintering time 8h,
Material air-isolation is cooled to normal temperature, weighs the weight of disengaging material, statistics burn tinctuer is 37.8%.Then cyclone vortex is used
Pulverizer is crushed, and obtains nickel-cobalt lithium manganate cathode material, the granularity (D of materialv50) it is 16.0 μm, specific surface area is
0.2m2/g。
Forerunner's body section Electron microscopic findings such as Fig. 1 described in embodiment 3 (accelerates high pressure EHT=10.00kV, working distance
From WD=10.3mm, multiplication factor Mag=3.00KX, Signal A=InLens) shown in, the results showed that：In precursor construction
In the presence of the discontinuous random space (about 1-2 μm of size) of some macro-scales.
Embodiment 4
From 1000L ceramic ball mills.Opening stirring, (30rpm, polyurethane ball material is with raw material weight than 1.3:1), stirring
381.0kg nickel cobalt manganese presoma (Ni is added in the case of mixing0.80Co0.11Mn0.09(OH)2, then weigh 159.8kg carbonic acid powder for lithium
Be added in ceramic ball mill, under agitation add 16.2kg K702 solution, and 0.27kg magnesia (content with into
Product meter content of magnesium is 400ppm), the water zirconium nitrates of 1.19kg five (content counts zirconium content as 600ppm using finished product), and 0.11kg oxygen
Change yttrium (content counts yttrium content as 200ppm using finished product), speed (10rpm) stirring 4h dischargings are further reduced after stirring 2h and are filtered out
It is standby that polyurethane ball forms the plaster material with certain forming degree.
Using ventilation 24m roller kilns.It is 800 DEG C to set heating zone temperature, is passed through (oxygen content volume under the conditions of oxygen-enriched air
Than for 70%, gas input 600m3/ h) above-mentioned plaster material is encased in ceramic alms bowl be sintered, sintering time 8h,
Material air-isolation is cooled to normal temperature, weighs the weight of disengaging material, statistics burn tinctuer is 35.3%.Then cyclone vortex is used
Pulverizer is crushed, and obtains nickel-cobalt lithium manganate cathode material, the granularity (D of materialv50) it is 6.0 μm, specific surface area is
0.61m2/g。
Comparative example 1
From 1000L plough batch mixers, stirring (20rpm) is opened, before adding 380.8kg nickel cobalt manganese under agitation
Drive body (Ni0.6Co0.19Mn0.21(OH)2, then weigh 182.4kg monohydrate lithium hydroxide powders and be added in plough batch mixer, stirring
141kg deionized waters are added by 80wt% solid contents in the case of mixing, speed (3-5rpm) stirring 4h is further reduced after stirring 2h
It is standby that discharging forms the plaster material with certain forming degree.
Using ventilation 24m roller kilns.It is 400 DEG C to set heating zone temperature, and being passed through oxygen-enriched air, (oxygen content volume basis is
45%, gas input 400m3/ h) under the conditions of above-mentioned plaster material be encased in ceramic alms bowl carry out first sintering, sinter
Time is 13h, and material air-isolation is cooled into normal temperature, weighs the weight of disengaging material, and statistics burn tinctuer is 39.1%.Then
Crushed with cyclone vortex pulverizer, humidity≤2% of air is controlled during crushing, obtains first sintering semi-finished product.
Using ventilation 24m roller kilns.It is 700 DEG C to set heating zone temperature, is passed through (oxygen content volume under the conditions of oxygen-enriched air
Than being calculated as 70%, gas input 600m3/ h) above-mentioned first sintering semi-finished product are encased in ceramic alms bowl carry out second and burn
Knot, sintering time 8h, normal temperature is cooled to by material air-isolation, weighs the weight of disengaging material, and statistics burn tinctuer is
3.6%.Then crushed with cyclone vortex pulverizer, obtain that there is final prepared product nickel-cobalt lithium manganate cathode material, material
Granularity (Dv50) it is 13.0 μm, specific surface area 1.52m2/g。
Comparative example 2
From 1000LY type mixers, stirring (35rpm) is opened, before adding 380.7kg nickel cobalt manganese under agitation
Drive body (Ni0.69Co0.14Mn0.16(OH)2, then weigh 220.3kg oxalic acid powder for lithium and be added in mixer, press under agitation
80wt% solid contents add 175kg deionized waters, and (content Ti content in terms of finished product is 0.21kg nano titanium oxides
400ppm), 0.31kg alundum (Al2O3)s (content counts aluminium content as 400ppm using finished product), speed is further reduced after stirring 2h
(3-5 turn/min) stirring 2h discharges, and to form the plaster material with certain forming degree standby.
Using ventilation 24m roller kilns.It is 500 DEG C to set heating zone temperature, and being passed through oxygen-enriched air, (oxygen content volume basis is
45%, gas input 400m3/ h) under the conditions of above-mentioned plaster material be encased in ceramic alms bowl carry out first sintering, sinter
Time is 15h, and material air-isolation is cooled into normal temperature, weighs the weight of disengaging material, and statistics burn tinctuer is 25.6%.Then
Crushed with cyclone vortex pulverizer, the humidity that air is controlled during crushing is 2%, obtains first sintering semi-finished product.
Using ventilation 24m roller kilns.It is 700 DEG C to set heating zone temperature, is passed through (oxygen content volume under the conditions of oxygen-enriched air
Than being calculated as 70%, gas input 600m3/ h) above-mentioned first sintering semi-finished product are encased in ceramic alms bowl carry out second and burn
Knot, sintering time 8h, normal temperature is cooled to by material air-isolation, weighs the weight of disengaging material, and statistics burn tinctuer is
2.9%.Then crushed with cyclone vortex pulverizer, obtain that there is final prepared product nickel-cobalt lithium manganate cathode material, material
Granularity (Dv50) it is 10.0 μm, specific surface area 0.32m2/g。
Comparative example 3
Comparative example 3 is similar with the embodiment of the present invention 1, differs only in, by polystyrene-based glucosyl group acroleic acid polymerization
Thing is changed to citric acid, addition 0.48kg, with the mass fraction of raw material is 0.05% based on active principle, material batch mixing and burning
Larger, the granularity (D of the material finally prepared of citric acid volatilization is found during knotv50) it is 13.0 μm, specific surface area is
0.32m2/g。
Comparative example 4
Comparative example 4 is similar with the embodiment of the present invention 1, differs only in, plus polystyrene base glucosyl group acroleic acid polymerization
The amount of thing is 55kg, and the mass fraction with raw material based on active principle is 10.1%, occurs significantly going out in mixing process
Nickel is showed, the Ion release phenomenon of cobalt ions characteristic color, material after material is encased in ceramic saggar drying course will have been mixed and glued
Chamber wall phenomenon is serious, and material occurs hardened and reunited, the granularity (D of the material finally preparedv50) it is 13.0 μm, specific surface area
For 1.51m2/g。
Positive electrode prepared by above-described embodiment carries out following signs：
1. scanning electron microscope sem figure
By above-described embodiment 4, comparative example 1, the positive electrode powder that comparative example 2 is prepared is scanned Electronic Speculum respectively
SEM is tested, and is obtained Fig. 2-a and (is accelerated high pressure EHT=15.00kV, operating distance WD=7.5mm, multiplication factor Mag=
10.00KX, Signal A=InLens), Fig. 2-b (accelerate high pressure EHT=15.00kV, operating distance WD=7.5mm, times magnification
Number Mag=10.00KX, Signal A=InLens) and Fig. 2-c (acceleration high pressure EHT=15.00kV, operating distance WD=
7.5mm, multiplication factor Mag=10.00KX, Signal A=InLens) result.
From Fig. 2-a, Fig. 2-b, Fig. 2-c, the comparative example and embodiment prepared using the same raw material of the technology of the present invention
There is larger difference on material morphology, embodiment 4, comparative example 1, the positive electrode that comparative example 2 is prepared is by once ball
The poly- secondary spherical structure formed of cluster, a ball particle in embodiment 4 is in the same size, is 0.15 μm or so, and comparative example 1,
A ball particle in comparative example 2 is not of uniform size, for secondary ball-type high-nickel material, size and the uniformity pair of a ball
There is large effect in the performance of material, consistent ball is too small, then material specific surface area is excessive, and the later stage, which sizes mixing, has gelatin phenomenon,
One time ball is excessive, then material conductivity is poor, and the lithium battery of preparation polarizes increase in de- lithium/process of intercalation, can have a strong impact on lithium
The service life of battery, and primary particle size matching shows that the embedding lithium degree of the body of material differs, it is possible in material surface
There is lithium phenomenon more than needed.Therefore using poly- polyacid process advan in the more preferable nickelic system's positive electrode of preparation structure.
Simultaneously from Fig. 2-a, Fig. 2-b, Fig. 2-c, occur on the particle surface of comparative example 1 without fine particulates, show it
Uncoated to have doped chemical, the positive electrode Surface coating that comparative example 2 is prepared has the uneven fine particle of size, compared
For, material surface prepared by embodiment 4 is smooth, and wrappage is evenly distributed.
2nd, free lithium and pH value
Example 1, embodiment 2, embodiment 3, embodiment 4, comparative example 1, each about 50g of comparative example 2, titrated using leaching
Free lithium content and pH value in method test contrivance.Concrete operations are：50g positive mixs are taken (code name m, unit g), to add about
100g deionized waters, 30min is stirred on magnetic stirring apparatus, then filtered and filtered with filter paper, 50ml liquid is weighed with pipette (50ml)
Body, put into the 100ml beakers with magnetic stirring apparatus.Beaker is placed in and is lined with the autotitrator of white circular filter paper, is dripped
Add 2 drop phenolphthalein indicators (0.1g/L ethanol solutions), generally now solution pinkiness.
Start to titrate with normal hydrochloric acid liquid (0.049mol/L, code name C, unit mol/L), when solution is changed into nothing from red
Color, record the hydrochloric acid solution volume V of consumption1(unit:ml).2 drop methyl reds are added dropwise into solution again, and (0.1g/L absolute ethyl alcohols are molten
Liquid) indicator, continues to titrate hydrochloric acid solution, until the color of solution is changed into orange from yellow.
Take out beaker and carry out boiling heating, caused carbon dioxide in solution is evaporated, solution returns again after cooling
In yellow.Remove after beaker is cooled to room temperature (23 ± 2 DEG C) and be further continued for volumetric soiutions, when solution is changed into pale red from yellow,
Record the volume V of hydrochloric acid standard solution2(unit:ml).Leaching liquid is converted into positive electrode dissociate lithium carbonate and lithium hydroxide
Cubage formula is as follows.
Li2CO3(wt%)=(V2-V1)*C*73.886*2*100/1000/m
LiOH (wt%)=[V2-2*(V2-V1)]*C*23.946*2*100/1000/m
Li+(wt%)=V2*C*6.94*2*100/m/1000
With reference to GB/T 9724-2007,5g embodiment samples add the 45g deionized waters of metering, stirred with clean magnetic agitation
30min is mixed, then time of repose 90min is filtered with filter paper, takes clear filtrate to detect the pH of filtrate with pH meter under the conditions of 23 ± 2 DEG C
Value, obtains the pH value of embodiment powder, the free lithium and pH value result of above-described embodiment are as shown in table 4.
The free lithium content of the embodiment of table 4 and pH test results
| Embodiment | Lithium hydroxide | Lithium carbonate | Always free lithium | PH value |
| Unit | (wt%) | (wt%) | (wt%) | --- |
| 1 | 0.0345 | 0.1462 | 0.0375 | 11.31 |
| 2 | 0.0377 | 0.1737 | 0.0435 | 11.27 |
| 3 | 0.0430 | 0.1376 | 0.0383 | 11.59 |
| 4 | 0.0365 | 0.1292 | 0.0353 | 11.65 |
| Comparative example 1 | 0.3447 | 1.0307 | 0.2985 | 11.75 |
| Comparative example 2 | 0.3643 | 1.0902 | 0.3105 | 11.80 |
| Comparative example 3 | 0.2710 | 0.8238 | 0.2330 | 11.95 |
| Comparative example 4 | 0.2548 | 0.5941 | 0.1865 | 11.95 |
From table 4, the free lithium content of the material prepared using the present invention is substantially reduced, close to common low nickel ternary material
The free lithium content of material, and corresponding pH is relatively low, the almost order of magnitude lower of the carbonic acid lithium content in especially free lithium.Generally
For high-nickel material because aerogenesis is seriously only used for preparing cylindrical type hard steel housing battery, cylindrical battery is sealingization generally after fluid injection
Into therefore caused gas is all sealed in box hat, as gas production is excessive, except security incident easily occurs in preparation process
Outside, it is possible to because Vent upsets cause battery failure (having output voltage no current, i.e., interior open circuit), and follow-up lithium battery applications
During potential safety hazard be present, therefore low free lithium material is more suitable for applying in cylindrical battery, if further improving, have can
Aerogenesis can be further reduced, promotes high-nickel material to be applied in flexible package lithium cell.Comparatively speaking, using the lemon of low molecule amount
Acid, and addition excessively can cause side effect to production technology, while can influence the preparation of material and the entrance of oxygen atmosphere,
Cause to prepare difficult, performance reduction.
3rd, full battery preparation and Performance Evaluation
By embodiment 1 to embodiment 4,6 positive electrode powders that comparative example 1 to comparative example 2 is prepared are as positive pole
Active material is prepared into capacity as 4.5-4.8Ah or so electrokinetic cell by the design of 21700 cylindrical batteries, with cylindrical battery during design
It is the standard (volume and total closing dischargeable capacity of cylindrical battery that i.e. active principle accounts in cylindrical battery to hold nargin with identical
Percentage, usually 96% or so).Full battery is made to be mainly used in investigating high voltage cycle and security impact.Wherein commented
It is the shaped steel housing battery of winding-structure 21700 to estimate applicable kind, and the cell diameter of making is 21mm, is highly 70mm.
Anode pole piece is prepared generally by preparing slurry, and coating and the technique such as cold pressing, cutting are made, and effective positive pole is lived in pole piece
Property content of material be 97.5%, pole coating average weight is 0.0260g/cm3, pole coating width is 62mm, and pole piece is active
The material gross area is 937.4cm2, Al foil substrate thickness is 13 μm, and pole piece compaction density is calculated as 3.2g/cm with active material3。
The preparation method of negative plate generally via slurry is prepared, is coated with, cold pressing, prepared by the process such as cutting.Using artificial stone
When ink is used as negative electrode active material, the effective negative electrode active material of pole piece (Delanium) content after preparation is 96.0%, pole piece
Coating weight is 0.0164g/cm2, pole coating width is 63.5mm, and the pole piece active material gross area is 1009.65cm2, copper foil
Base material thickness is 9 μm, and pole piece compaction density is calculated as 1.65g/cm with active material3。
The positive plate of aluminium pole ears will be welded with, (thickness to be handled through nano aluminium oxide is 16 μm of PP/PE/ to barrier film
PP composite isolated films), it is welded with negative plate of nickel lug etc. and winds in order and be prepared into the naked battery core of cylinder, and lug is put absolutely
Enter shell after edge ring, using laser welding by nickel tab welding in cylinder bottom, be then prepared into the reeded naked battery core of tool through curling,
Fluid injection is cooled down after drying, and lug is being welded to the protection component such as CID, PTC and Vent successively, is encapsulated after standing in LIP-
10AHB06 types high temperature chemical conversion machine chemical conversion (formation voltage 0~4.2V, 0.1C charging, 0.2C electric discharges, temperature 45 C ± 2 DEG C), is carried out
Volume test (test voltage 3.0~4.2V, 0.2C, 0.5C), select up-to-standard battery core and be used for follow-up Performance Evaluation.
By embodiment 3, embodiment 4, lithium battery prepared by comparative example 2 is put into 60 DEG C of baking ovens, and electrode is linked into LIP-
1C/1C is carried out on 10AHB06 type high temperature chemical conversion machines, 3.0-4.2V cycle detections, obtains Fig. 3 high temperature circulation result.Can by Fig. 3
To see, cycle performance of lithium ion battery prepared by example of the present invention is excellent, through 500 weeks circulation volume conservation rates still greater than 75%, its
The capability retention of middle embodiment 3 was more than 90% in circulation in 500 weeks, had exceeded high-nickel material conventional detection result.Comparative example 2 is made
Standby lithium ion battery circulation linearly declines, and capacity attenuation is very fast.
4th, safe drift bolt test
Embodiment 1, embodiment 2, embodiment 3, the positive electrode preparation that comparative example 1 and comparative example 3 make are used by above-mentioned
21700 type cylinder type lithium ion secondary batteries carried out by QC/T 743-2006 (electric road vehicle with lithium-ions battery)
Nail thorn (nail diameter of phi 8mm, puncture speed is 20~25mm/s), overcharges (constant-current charge to 200% rated capacity) test, will examine
Survey every group of qualified lithium battery electric core and take 2-3 only, the constant temperature 2h under room temperature condition (23 DEG C ± 2 DEG C), then in LIP-10AHB06
3.0V is discharged to by 0.5C on type high temperature chemical conversion machine, discharge off stands 30s, takes out battery core detection battery core thickness, internal resistance etc. and refers to
Mark, then restocking charges to 4.2V by 0.5C again, then using 20mA low currents CV to blanking voltage as 4.2V, retrieve amount of batteries
Thickness Measurement by Microwave, terminal voltage and internal resistance, battery core is then stood 2 hours and tested by standard, obtained such as Fig. 4-a (embodiment 1), figure
4-b (comparative example 1) and the representative result shown in table 5.
The embodiment of table 5 nail thorn result of the test
From Fig. 4-a and Fig. 4-b, under the lithium battery nail thorn abuse condition prepared using example 1 of the present invention and comparative example 1
Can be by the way that heated up equal unobvious, but the lithium battery of the preparation of comparative example 1 temperature and voltage in test is extremely unstable, and curve is presented
Lower fluctuation status, show be probably in test process some protection structures in action.Simultaneously from table 5, the electricity of comparative example 1
It increased dramatically after the inner walkway of core, actually lost the use condition as reversible lithium ion battery.So this
Drift bolt experiment can by be mainly cylindrical battery component in action, comparative example 1 prepare material deposit in use
In larger security risk, so that side demonstrates technical scheme.
The embodiment of the present invention is described above by embodiment, it will be understood by those skilled in the art that on
Literary embodiment is merely for the purpose of citing, it is not considered that limiting the protection domain of the present invention with this, those skilled in the art are not
Depart from the premise of present invention spirit that it can be modified, change or replacement, still, made according to the present invention various etc.
With change, the scope that the present invention is covered is still fallen within.
In summary, positive electrode surface of the present invention forms the bulk phase-doped layer of stable uniform, can avoid positive pole
Material powder granule during later stage use directly contacts with electrolyte, so as to be advantageous to nickelic positive electrode in high voltage,
Use in long circulating system, while improve the security performance of lithium battery.Preparation method economically feasible of the present invention, operation
Simply, positive effect, there is preferable application prospect.
Claims (16)
- A kind of 1. anode material for lithium-ion batteries, it is characterised in that chemical formula LixNiaCobMncRdO2Wherein, R is doping member Element, 0.95 ＜ x ＜, 1.15,0.5 ＜ a ＜ 1.0,0 ＜ b ＜ 0.2,0.0≤c≤0.3, a+b+c=1,0≤d ＜ 0.1；Wherein, institute State the mass fraction ＞ 30% that nickel element accounts for positive electrode, preferably ＞ 40%.
- 2. positive electrode according to claim 1, wherein, the free lithium of the positive electrode accounts for the mass fraction of positive electrode More than 0, it is less than 0.5% less than 1%, preferably greater than 0, it is furthermore preferred that to be less than 0.2% more than 0.
- 3. positive electrode according to claim 1 or claim 2, wherein, the lithium hydroxide that dissociates in the positive electrode accounts for positive electrode Mass fraction be more than 0 be less than 0.3%, preferably greater than 0 be less than 0.1%, it is furthermore preferred that for more than 0 be less than 0.05%.
- 4. according to any one of the claim 1-3 positive electrodes, wherein, the free carbonic acid lithium of the positive electrode accounts for positive pole material The mass fraction of material is more than 0 and is less than 1%, and preferably greater than 0 is less than 0.5%, it is furthermore preferred that to be less than 0.2% more than 0.
- 5. the preparation method of anode material for lithium-ion batteries described in claim 1, it is characterised in that comprise the steps：By the raw material including presoma, Li source compound, doping element compound and macromolecule acids polymers by metering than mixed After conjunction, the anode material for lithium-ion batteries is obtained through oversintering；Wherein, the presoma chemical formula is NiaCobMncRd(OH)2, wherein, R is doped chemical, the ＜ b ＜ of 0.5 ＜ a ＜ 1.0,0 0.2,0.0≤c≤0.3, a+b+c=1,0≤d ＜ 0.1；The positive electrode chemical formula is LixNiaCobMncRdO2Wherein, 0.95 ＜ x ＜ 1.15, nickel element account for the mass fraction ＞ 30% of positive electrode, preferably ＞ 40%；The macromolecule acids polymers contain acidic-group；Relative molecular mass is 3000-4000000.
- 6. preparation method according to claim 5, wherein, the macromolecule acids polymers account for raw material based on effective ingredient Mass fraction is 0.1-10%.
- 7. according to the preparation method of claim 5 or 6, wherein, in the macromolecule acids polymers, acidic-group accounts for high score The mass fraction of sub- acids polymers is 23%-63%.
- 8. according to any one of the claim 5-7 preparation methods, wherein, the macromolecule acids polymers are selected from acrylic compounds Polymer, the acrylic polymer are selected from polyacrylic acid, styrene acrylic based polyalcohol or polystyrene-based grape The one or more of glycosyl acrylate copolymer, preferably acrylic acid polymer and/or polystyrene-based glucosyl group Acrylate copolymer.
- 9. according to any one of the claim 5-8 preparation methods, wherein, the doped chemical be selected from aluminium, magnesium, zirconium, titanium, tungsten, It is more than one or both of lanthanum or yttrium.
- 10. according to any one of the claim 5-9 preparation methods, wherein, the Li source compound is selected from containing lithium hydroxide, grass It is more than one or both of sour lithium, lithium carbonate, lithium nitrate, lithium acetate, lithium fluoride, lithium chloride, tert-butyl alcohol lithium or lithium citrate.
- 11. according to any one of the claim 5-10 preparation methods, wherein, the raw material also includes water, and water accounts for the matter of raw material Amount fraction is 0-30%.
- 12. according to any one of the claim 5-11 preparation methods, wherein, the sintering temperature is 700-880 DEG C, sinters gas Atmosphere is oxygen-enriched air, and oxygen volume content is 50-70%, and roasting time is 5-10 hours.
- 13. the preparation method according to claim 11, wherein, the mixture for adding the preparation of water raw material, in the roasting Before burning process, include the process of pre-burning, the burn-in process comprises the steps：At 200-500 DEG C, under conditions of oxygen volume ratio is 40%-65%, 5-20 hours are sintered.
- 14. a kind of anode material for lithium-ion batteries, it is characterised in that prepared by any one of the claim 5-13 preparation methods Obtain.
- 15. a kind of lithium ion battery, it is characterised in that include any one of claim 1-4 or claim 14 the positive pole material Material.
- 16. lithium ion battery described in any one of claim 1-4 or claim 14 positive electrode or claim 15 exists The application of lithium electric energy source domain.
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