CN103647073B - A kind of anode material for lithium-ion batteries and preparation method thereof - Google Patents
A kind of anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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- CN103647073B CN103647073B CN201310699023.1A CN201310699023A CN103647073B CN 103647073 B CN103647073 B CN 103647073B CN 201310699023 A CN201310699023 A CN 201310699023A CN 103647073 B CN103647073 B CN 103647073B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- 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 discloses the preparation method of a kind of anode material for lithium-ion batteries, described method is successively at outer surface coated aluminum oxide layer and the carbon-coating of existing anode material for lithium-ion batteries, capsulation condition is liquid phase coating, during carrying out alumina-coated, have adjusted the addition sequence of existing anode material for lithium-ion batteries and aluminium salt, by being stirred continuously during adding cladding material organic aluminium salt, it is ensured that hydrolyzate uniform adsorption is at active material surface.Described method is by being spray-dried and the method for Fast Sintering under an inert atmosphere carries out carbon cladding, it is possible to avoids pyrocarbon cladding to be easily caused metal and reduces, the problem that low temperature organic carbon source is difficult to carbonization.Meanwhile, invention additionally discloses a kind of anode material for lithium-ion batteries using method as defined above to prepare, it is possible to significantly improve energy density and the power density of battery, and the cycle performance of battery, capability retention and security performance can be improved.
Description
Technical field
The present invention relates to field of lithium ion battery, especially a kind of Olivine-type Cathode Material in Li-ion Batteries and system thereof
Preparation Method.
Background technology
The eighties in 20th century, American scholar J.B.Goodenough et al. finds cobalt acid lithium (LiCoO first2),
Lithium nickelate (LiNiO2) and LiMn2O4 (LiMn2O4) can be as the material of deintercalate lithium ions.20th century 90
In the age, cobalt acid lithium is the most successfully applied to business-like small-sized electronic product by Sony, from this, lithium-ion electric
Pond is widely used in each electronic equipment with advantages such as high cycle performance, high working voltage and low stain.Closely
Nian Lai, along with science and technology development, the function of electronic equipment is constantly upgraded, therefore energy and the multiplying power to lithium battery
Performance is had higher requirement, the most conventional cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4) with
And three element materials, its capacity and power are difficult to meet electronic equipment that function constantly upgrades to high-energy-density
And the requirement of big multiplying power discharging, therefore high energy and high power lithium ion cell have become the emphasis of battery industry and have ground
Study carefully direction.
One of key technology of high-performance lithium ion battery is research and development high-performance positive electrodes, in lithium ion battery,
The performance of positive electrode largely affects the performance of lithium ion battery, and directly determines the cost of battery.
The energy and the power that improve battery from positive electrode generally have two kinds of methods: one is the charged electrical improving battery
Pressure, generally fills up to 4.30V or 4.35V, battery phase by the charge cutoff voltage of lithium ion battery from 4.20V
The discharge capacity answered improves 8%～14%, it is possible to be effectively improved the energy density of battery；Two is to improve material certainly
The electric conductivity of body thus improve the power density of battery.
For above method one, under high charge blanking voltage (＞ 4.20V), such as plain edition positive electrode
LiCoO2The lithium ion of middle unit mole is moved out ＞ 0.5, easily causes cathode material structure unstable, shows as
The instability of lithium ion battery and cycle performance sharp-decay.The quantivalence of Co when this is primarily due to uncharged
For+trivalent, and the Co taking off lithium state when charging is+4 valencys, and the Co of+4 valencys has the strongest oxidisability, it is possible to
React with electrolyte, make cathode material structure change even to cave in also result in electrolyte decomposition.Therefore
The premise of the charge cutoff voltage improving lithium ion battery is that positive electrode is carried out surface process, such as cladding.
And conventional method for coating is at positive electrode Surface coating Al2O3Deng metal-oxide, be conducive to stablizing positive pole
The structure of material also stops directly contacting of positive active material and electrolyte.But it is generally used for surface coated
Oxide (Al2O3Deng) it is insulant, the electric conductivity reducing material is processed through cladding, so that electric
The power in pond reduces.
And for above method two, improving the electric conductivity of material, conventional method is to add conductive agent (carbon dope)
With the method that positive electrode is carried out carbon cladding.The method of carbon dope is mainly mechanical mixing at present, and mechanical
It is long to there is the operating time in mixing method, mixes the shortcomings such as uneven；Carbon cladding can be effectively improved the conduction of material
Property, improve the surface chemistry of active material, avoid electrode directly and electrolyte contacts, it is possible to increase electrode
Fast charging and discharging performance and cycle performance；And conventional anode material for lithium-ion batteries (cobalt acid lithium, LiMn2O4
Or three element materials etc.) synthesis condition be in air or oxygen atmosphere, synthesis temperature more than 900 DEG C,
Under the conditions of such, carbon occurs oxidation to be difficult to carbon cladding, therefore, it is achieved carbon cladding needs indifferent gas
Under atmosphere；It addition, carbon decomposes and graphitization temperature is up to 600～900 DEG C, it is easy to by gold such as nickel, cobalt, manganese
Belonging to ion reduction and become simple substance, the most traditional is difficult to carbon cladding by Organic carbon decomposition.
Summary of the invention
There is provided the one can be at existing lithium in place of it is an object of the invention to overcome above-mentioned the deficiencies in the prior art
Ion battery positive electrode surface coated aluminum oxide layer and the Olivine-type Cathode Material in Li-ion Batteries system of carbon-coating successively
Preparation Method；Meanwhile, further object is that offer one uses method described above to prepare
, the energy density that battery can be significantly improved and power density and can improve battery cycle performance and
The Olivine-type Cathode Material in Li-ion Batteries of security performance.
For achieving the above object, the technical scheme that the present invention takes is: a kind of anode material for lithium-ion batteries
Preparation method, comprises the following steps:
(1) existing anode material for lithium-ion batteries A is synthesized in conventional manner；
(2) anode material for lithium-ion batteries A and solvent S is configured to slurry, under conditions of being stirred continuously
It is gradually added into rubbing of aluminum and anode material for lithium-ion batteries A in aluminum salt solution or colloidal sol, aluminum salt solution or colloidal sol
Your ratio is 0.002～0.02；
(3) mixed liquor of step (2) was dried through 4～24 hours in 70～100 DEG C after filtering, sieves,
Powder at 300～600 DEG C in air or oxygen atmosphere roasting 4～8 hours, obtain through sieving after natural cooling
Outer surface is coated with the anode material for lithium-ion batteries of alumina layer B；
(4) anode material for lithium-ion batteries that outer surface is coated with alumina layer B is configured to deionized water
Mixed liquor, whipping process adds organic carbon source in mixed liquor, is stirred until homogeneous mixing；
(5) by step (4) gained mixed liquor by obtaining at alumina layer B appearance bread after being spray-dried
Covering the lithium ion battery positive material powder of organic carbon, the inlet temperature of spray drying is 100～200 DEG C, outlet
Temperature is 50～80 DEG C；
(6) powder step (5) obtained loads crucible and is placed in tube furnace, and evacuation, by lazy
Property atmosphere, under inert atmosphere conditions heating 600～800 DEG C of roastings 0.5～2h, obtain through sieving after natural cooling
Outer surface is coated with alumina layer B and the anode material for lithium-ion batteries of carbon-coating C successively.
The preparation method of anode material for lithium-ion batteries of the present invention, successively at existing lithium ion cell positive
The outer surface coated aluminum oxide layer of material and carbon-coating, capsulation condition is liquid phase coating, is readily obtained ratio more uniform
Cladding.The method of the invention, during carrying out alumina-coated, have adjusted existing lithium ion battery
Positive electrode and the addition sequence of aluminium salt, the most first disperse active substance in a solvent, and dispersion liquid itself is in alkali
Property, a small amount of cladding material aluminium salt and the addition of solvent are little on its alkalescence impact；By having at addition cladding material
It is stirred continuously during machine aluminium salt, it is ensured that hydrolyzate uniform adsorption is at active material surface.Described method
It can be avoided that pyrocarbon cladding is easily caused metal reduction, low temperature organic carbon source is difficult to the problem of carbonization, passes through
The method of spray drying under an inert atmosphere Fast Sintering carries out carbon cladding.
The mol ratio choosing of aluminum and anode material for lithium-ion batteries A in aluminum salt solution or colloidal sol in described step (2)
Select 0.002～0.02, if aluminum is at the bag of anode material for lithium-ion batteries A outer surface in aluminum salt solution or colloidal sol
Cover very little, cannot well play the effect of protective layer；If too many, the gram volume of material can be affected.
As the preferred implementation of the preparation method of anode material for lithium-ion batteries of the present invention, described step
Suddenly the solvent S in (2) is the mixture of water and organic solvent that can be miscible with water, described organic solvent and water
Weight ratio be 0～100；The mass ratio of described anode material for lithium-ion batteries A and solvent S is 0.5:1～5:1.
Preferably, described organic solvent is alcohols or ketones solvent.Described organic solvent is 0～100 with the weight ratio of water,
The most described solvent S can select water, or the mixed liquor of water and organic solvent.Described lithium ion cell positive
Materials A selects 0.5:1～5:1, to ensure that described anode material for lithium-ion batteries A can with the mass ratio of solvent S
With with solvent S-shaped form slurry.
As the preferred implementation of the preparation method of anode material for lithium-ion batteries of the present invention, described step
Suddenly in (2), the weight concentration of aluminum salt solution or colloidal sol is 10～50%, in described aluminum salt solution or colloidal sol, molten
Agent is the solvent that can dissolve aluminium salt, it is preferable that can be water or can organic solvent miscible with water or water and can be with
The mixed liquor of the organic solvent that water dissolves each other.Preferably, described solvent is alcohols or ketones solvent.Described aluminium salt
The weight concentration of solution or colloidal sol selects 10～50%, and concentration is the lowest, the problem that can there is waste solvent, and dense
Du Taigao, is easily caused, in the moment that aluminum salt solution or colloidal sol add, the problem that local concentration is the biggest.
As the preferred implementation of the preparation method of anode material for lithium-ion batteries of the present invention, described step
Suddenly, in the aluminum salt solution of (2) or colloidal sol, aluminium salt is at least one in an aluminium acetate, oxalic acid aluminum.
As the preferred implementation of the preparation method of anode material for lithium-ion batteries of the present invention, described step
Suddenly in (2), the addition speed of aluminum salt solution or colloidal sol is 1～20ml/min.Add speed too slow, conventional efficient
Low, and it is too fast to add speed, can cause being coated with uneven.
As the preferred implementation of the preparation method of anode material for lithium-ion batteries of the present invention, described step
Suddenly, after (2) are gradually added into aluminum salt solution or colloidal sol under conditions of being stirred continuously, stirring 1～4 hour is continued,
Mixing speed is 200～2000r/min.In described step (2), after adding aluminum salt solution and colloidal sol, continue
Continue and stir 1～4 hour according to described mixing speed, it is possible to make aluminum salt solution or colloidal sol and existing lithium ion
Cell positive material A is mixed homogeneously with solvent S so that aluminium oxide is at existing anode material for lithium-ion batteries A
The cladding of outer surface is more uniform.
As the preferred implementation of the preparation method of anode material for lithium-ion batteries of the present invention, described step
Suddenly (4) outer surface is coated with the anode material for lithium-ion batteries of alumina layer B and the mass ratio of deionized water
For 0.5:1～2.5:1.Outer surface is coated with anode material for lithium-ion batteries and the deionized water of alumina layer B
Why mass ratio selects described scope, is to ensure that complete machine material can well form slurry with solvent
Material, and use, from the most different carbon claddings, the mode being spray-dried, suitably concentration limit can be improved one
Point, because spray resistance is big if concentration is the lowest, may not reach the effect of spraying.
As the preferred implementation of the preparation method of anode material for lithium-ion batteries of the present invention, described step
The quality of the organic carbon source suddenly added in (4) is the lithium ion cell positive that outer surface is coated with alumina layer B
The 2～20% of quality of materials.Very little, cladding does not the most just have and improves electric conductivity the addition of organic carbon source
Effect, and addition is too many, cladding can affect again the gram volume of material too much.
As the preferred implementation of the preparation method of anode material for lithium-ion batteries of the present invention, described step
Suddenly the inert atmosphere in (6) is nitrogen atmosphere or helium atmosphere.
Meanwhile, another object of the present invention is to provide a kind of energy density that can significantly improve battery and merit
Rate density and the cycle performance of battery and the Olivine-type Cathode Material in Li-ion Batteries of security performance can be improved,
For realizing this purpose, the technical scheme that the present invention takes is: a kind of arbitrary described method of employing is prepared into
The anode material for lithium-ion batteries arrived, described anode material for lithium-ion batteries includes existing lithium ion cell positive
Materials A, it is coated on the alumina layer B of described anode material for lithium-ion batteries outer surface and is coated on described oxygen
Change the carbon-coating C of aluminium lamination outer surface.Anode material for lithium-ion batteries of the present invention, at existing lithium ion battery just
The outer surface of pole material is coated with alumina layer and carbon-coating successively, and wherein, the cladding of alumina layer can reduce
Positive electrode contacts with electrolyte, effectively stops the reaction of positive electrode and electrolyte, improves lithium-ion electric
Pond cycle performance, overcharging resisting performance and storge quality under high charge blanking voltage；Through coated aluminum oxide
Material carry out carbon cladding again, it is possible to prevent positive electrode and carbon catabolite generation redox reaction, with
Time carbon cladding can form uniform conductive film on positive electrode surface, improve the electric conductivity of positive electrode,
Be conducive to quickly embedding and abjection of lithium ion, thus improve the high rate during charging-discharging of battery.
The preparation method of anode material for lithium-ion batteries of the present invention and use the lithium that described method prepares
In ion battery positive electrode, described existing anode material for lithium-ion batteries A can be nickel, cobalt, manganese binary
Or tertiary cathode material, lithium cobaltate cathode material, manganate cathode material for lithium (containing the stratiform rich lithium LiMn2O4 of doping,
Spinel lithium manganate) etc..
The preparation method of anode material for lithium-ion batteries of the present invention, uses liquid phase coating successively at existing lithium
The outer surface coated aluminum oxide layer of ion battery positive electrode and carbon-coating, it is possible to obtain than more uniform cladding.
During carrying out alumina-coated, have adjusted the addition sequence of existing anode material for lithium-ion batteries and aluminium salt,
The most first being disperseed in a solvent by active substance, dispersion liquid itself, in alkalescence, is coated with material aluminium salt and solvent on a small quantity
Addition on its alkalescence impact little, by add cladding material organic aluminium salt process be stirred continuously, it is ensured that
Hydrolyzate uniform adsorption is at active material surface.Described method is by being spray-dried and the fastest
The method of speed sintering carries out carbon cladding, it is possible to avoiding pyrocarbon cladding to be easily caused metal reduction, low temperature is organic
The problem that carbon source is difficult to carbonization.The method of the invention, produces without harmful intermediate product in processing procedure,
Meet the modern industry requirement to environmental conservation.
Use the anode material for lithium-ion batteries that the method for the invention prepares, at existing lithium ion battery
The outer surface of positive electrode is coated with alumina layer and carbon-coating successively, and alumina-coated can reduce positive electrode
With contacting of electrolyte, effectively stop the reaction of positive electrode and electrolyte, improve lithium ion battery and fill at height
Cycle performance, overcharging resisting performance and storge quality under electricity blanking voltage；Through coated aluminum oxide material again
Carry out carbon cladding, it is possible to prevent positive electrode and carbon catabolite generation redox reaction, simultaneously carbon cladding
Uniform conductive film can be formed on positive electrode surface, improve the electric conductivity of positive electrode, be conducive to
Quickly embedding and abjection of lithium ion, thus improve the high rate during charging-discharging of battery.Lithium of the present invention
Ion battery positive electrode can significantly improve energy density and the power density of battery, and can improve battery
Cycle performance, capability retention and security performance.
Accompanying drawing explanation
Fig. 1 is the process chart of method for preparing anode material of lithium-ion battery of the present invention；
Fig. 2 is LiCoO after the embodiment of the present invention 1 cladding2Material 4.35V curve of double curvature figure；
Fig. 3 is LiCoO after comparative example 1 of the present invention cladding2Material 4.35V curve of double curvature figure；
Fig. 4 is existing uncoated LiCoO in the embodiment of the present invention 12Material 4.35V curve of double curvature figure.
Detailed description of the invention
For better illustrating the object, technical solutions and advantages of the present invention, below in conjunction with the accompanying drawings and be embodied as
The invention will be further described for example.
The specific embodiment of the preparation method of anode material for lithium-ion batteries of the present invention, the work of described method
As shown in Figure 1, described method specifically includes following steps to process flow figure:
(1) synthesizing existing anode material for lithium-ion batteries A in conventional manner, described existing lithium ion battery is just
Pole materials A can be specifically lithium cobaltate cathode material；Nickel, cobalt, manganese binary or tertiary cathode material；Mangaic acid
Lithium anode material (doping containing stratiform rich lithium LiMn2O4, spinel lithium manganate)；
(2) anode material for lithium-ion batteries A and solvent S is configured to slurry by the mass ratio of 0.5:1～5:1,
Being gradually added into weight concentration with the speed of 1～20mL/min under conditions of being stirred continuously is 10%～50% 1
Aluminium acetate or oxalic acid aluminum solutions, in aluminium salt the mol ratio of aluminum and anode material for lithium-ion batteries A be 0.002～
0.02, the speed with 200～2000r/min continues stirring 1～4 hour；
(3) mixed liquor of step (2) was dried through 4～24 hours in 70～100 DEG C after filtering, sieves,
Powder air or oxygen atmosphere roasting 4～8 hours, obtains through sieving after natural cooling at 300～600 DEG C
Outer surface is coated with the anode material for lithium-ion batteries of alumina layer B；
(4) outer surface is coated with the anode material for lithium-ion batteries of alumina layer B and deionized water by
The mass ratio of 0.5:1～2.5:1 is configured to mixed liquor, and whipping process adds outer surface cladding aerobic in mixed liquor
Change the organic carbon source of the anode material for lithium-ion batteries quality 2%～20% of aluminium lamination B, be stirred until homogeneous mixing；
(5) by step (4) gained mixed liquor by obtaining at alumina layer B appearance bread after being spray-dried
Covering the lithium ion battery positive material powder of organic carbon, the inlet temperature of spray drying is 100～200 DEG C, goes out
Mouth temperature is 50～80 DEG C；
(6) powder step (5) obtained loads crucible and is placed in tube furnace, and evacuation is passed through nitrogen
Gas or argon gas atmosphere, heat 600～800 DEG C of roastings 0.5～2h under nitrogen or argon gas atmosphere are protected, the coldest
But obtain outer surface after through sieving and be coated with carbon-coating C and the anode material for lithium-ion batteries of alumina layer B successively.
Embodiment 1
A kind of embodiment of the preparation method of a kind of anode material for lithium-ion batteries of the present invention, described in the present embodiment
Method comprises the following steps:
(1) LiCoO that 2000g synthesizes in conventional manner is weighed2Positive electrode A, add 1000g go from
The speed of sub-water 1500r/min is sufficiently stirred for, and drips in whipping process speed with 8mL/min in dispersion liquid
The 331.20g of addition deionized water dissolving (CH Han 33.12g3COO)2The solution of AlOH, after dripping,
Continue stirring 3 hours, stop stirring；
(2) 200 mesh sieves are crossed, then by dry powder in Muffle after filtering and be dried 20 hours in 80 DEG C
Roasting 5 hours under 500 DEG C of air atmospheres in stove, natural cooling obtains outer surface and is coated with alumina layer B's
LiCoO2Positive electrode；
(3) 2000g outer surface is coated with the LiCoO of alumina layer B2Positive electrode is joined with 1000g water
Making mixed liquor, whipping process adds 200g sucrose in mixed liquor, is stirred until homogeneous mixing；
(4) by be spray-dried after obtain alumina layer B outer surface cladding organic carbon lithium ion battery just
Pole material powder, the inlet temperature of spray drying is 100 DEG C, and outlet temperature is 60 DEG C；
(5) powder loads crucible to be placed in tube furnace, through continuous three evacuation and logical nitrogen procedure,
700 DEG C of roasting 1h under nitrogen protection, obtain outer surface and are coated with aluminium oxide successively through sieving after natural cooling
Layer B and the LiCoO of carbon-coating C2Positive electrode.
Embodiment 2
A kind of embodiment of the preparation method of a kind of anode material for lithium-ion batteries of the present invention, described in the present embodiment
Method comprises the following steps:
(1) LiCoO that 2000g synthesizes in conventional manner is weighed2Positive electrode A, add 500g go from
The speed of sub-water 2000r/min is sufficiently stirred for, and drips in whipping process speed with 1mL/min in dispersion liquid
The 101.40 of addition deionized water dissolving CH Han 50.70g3COOAl(OH)2Solution, after dripping, continue
Continuous stirring 4 hours, stops stirring；
(2) 200 mesh sieves are crossed, then by dry powder horse after filtering and be dried 24 hours in 100 DEG C
Not roasting 8 hours under 600 DEG C of air atmospheres in stove, natural cooling obtains outer surface and is coated with alumina layer B
LiCoO2Positive electrode；
(3) 2000g outer surface is coated with the LiCoO of alumina layer B2Positive electrode is joined with 1000g water
Making mixed liquor, whipping process adds 400g sucrose in mixed liquor, is stirred until homogeneous mixing；
(4) by obtaining the lithium ion battery at alumina layer B outer surface cladding organic carbon after being spray-dried
Positive electrode powder, the inlet temperature of spray drying is 150 DEG C, and outlet temperature is 80 DEG C；
(5) powder loads crucible to be placed in tube furnace, through continuous three evacuation and logical nitrogen mistake
Journey, under nitrogen protection 800 DEG C of roasting 2h, obtain outer surface and be coated with aerobic successively through sieving after natural cooling
Change aluminium lamination B and the LiCoO of carbon-coating C2Positive electrode.
Embodiment 3
A kind of embodiment of the preparation method of a kind of anode material for lithium-ion batteries of the present invention, described in the present embodiment
Method comprises the following steps:
(1) LiCoO that 2000g synthesizes in conventional manner is weighed2Positive electrode A, add 4000g go from
The speed of sub-water 2000r/min is sufficiently stirred for, and in whipping process speed with 20mL/min in dispersion liquid
It is added dropwise to 66.20g (CH Han 6.62g of deionized water dissolving3COO)2The solution of AlOH, after dripping,
Continue stirring 1 hour, stop stirring；
(2) 200 mesh sieves are crossed, then by dry powder in Muffle after filtering and be dried 4 hours in 70 DEG C
Roasting 6 hours under 400 DEG C of air atmospheres in stove, natural cooling obtains outer surface and is coated with alumina layer B's
LiCoO2Positive electrode；
(3) 2000g outer surface is coated with the LiCoO of alumina layer B2Positive electrode is joined with 4000g water
Making mixed liquor, whipping process adds 100g sucrose in mixed liquor, is stirred until homogeneous mixing；
(4) by obtaining the lithium ion battery at alumina layer B outer surface cladding organic carbon after being spray-dried
Positive electrode powder, the inlet temperature of spray drying is 200 DEG C, and outlet temperature is 80 DEG C；
(5) powder loads crucible to be placed in tube furnace, through continuous three evacuation and logical nitrogen mistake
Journey, under nitrogen protection 600 DEG C of roasting 0.5h, obtain outer surface and be coated with aerobic successively through sieving after natural cooling
Change aluminium lamination B and the LiCoO of carbon-coating C2Positive electrode.
Embodiment 4
A kind of embodiment of the preparation method of a kind of anode material for lithium-ion batteries of the present invention, described in the present embodiment
Method comprises the following steps:
(1) LiNi that 2000g synthesizes in conventional manner is weighed0.5Co0.2Mn0.3O2Positive electrode A, adds
The speed of 1000g deionized water 1500r/min is sufficiently stirred for, and whipping process in dispersion liquid with 8mL/min
Speed be added dropwise to the 335.80g (CH Han 33.58g with deionized water dissolving3COO)2The solution of AlOH, drips
After adding, continue stirring 3 hours, stop stirring；
(2) 200 mesh sieves are crossed, then by dry powder in Muffle after filtering and be dried 20 hours in 80 DEG C
Roasting 5 hours under 500 DEG C of air atmospheres in stove, natural cooling obtains outer surface and is coated with alumina layer B's
LiNi0.5Co0.2Mn0.3O2Positive electrode；
(3) 2000g outer surface is coated with the LiNi of alumina layer B0.5Co0.2Mn0.3O2Positive electrode with
1000g water is configured to mixed liquor, and whipping process adds 200g sucrose in mixed liquor, is stirred until homogeneous mixing；
(4) by obtaining the lithium ion battery at alumina layer B outer surface cladding organic carbon after being spray-dried
Positive electrode powder, the inlet temperature of spray drying is 120 DEG C, and outlet temperature is 80 DEG C；
(5) powder loads crucible to be placed in tube furnace, through continuous three evacuation and logical nitrogen mistake
Journey, under nitrogen protection 700 DEG C of roasting 1h, obtain outer surface and be coated with aerobic successively through sieving after natural cooling
Change aluminium lamination B and the LiNi of carbon-coating C0.5Co0.2Mn0.3O2Positive electrode.
Comparative example 1
Weigh the LiCoO that 2000g synthesizes in conventional manner2Positive electrode A, adds 1000g deionized water
The speed of 2000r/min is sufficiently stirred for, and is added dropwise in whipping process speed with 8mL/min in dispersion liquid
With the 331.20g of deionized water dissolving (CH Han 33.12g3COO)2The solution of AlOH, after dripping, continues
Stir 3 hours, stop stirring, filter, and be dried after 24 hours in 100 DEG C and cross 200 mesh sieves, then will
The powder being dried roasting 5 hours under 500 DEG C of air atmospheres in Muffle furnace, natural cooling obtains outer surface cladding
There is the LiCoO of alumina layer B2Positive electrode.
The nothing that the positive electrode that above example 1～embodiment 4 and comparative example 1 prepare synthesizes with conventional method
Clad anode material is ratio and the organic solvent of 95:2.5:2.5 respectively in mass ratio with conductive carbon black, binding agent
N-Methyl pyrrolidone is applied on aluminium foil after stirring, and dried and graphite cathode is fabricated to 68430
Battery also carries out gram volume, high rate performance and cycle performance test respectively, and chemical property contrasts respectively such as table 1
Shown in table 2:
Table 1
The cladded type LiCoO that embodiment 1, comparative example 1 obtain2LiCoO before positive electrode and cladding2Positive pole
68430 batteries of material, its high pressure curve of double curvature figure is the most as shown in Figure 2, Figure 3 and Figure 4.
Table 2
To sum up data are it can be seen that contrast with existing uncoated anode material for lithium-ion batteries, use this
The anode material for lithium-ion batteries that bright anode material for lithium-ion batteries material preparation method obtains, surface shape successively
Become aluminium oxide and carbon coating layer, it is possible to minimizing positive electrode contacts with electrolyte, effectively stops positive electrode
With the reaction of electrolyte, improve lithium ion battery cycle performance under high charge blanking voltage and storage volume
Conservation rate；Meanwhile, carbon cladding can improve the electric conductivity of positive electrode, improves the heavy-current discharge of battery
Performance.
Last institute is it should be noted that, above example is only in order to illustrate technical scheme rather than to this
The restriction of invention protection domain, although the present invention being explained in detail with reference to preferred embodiment, this area
It is to be appreciated by one skilled in the art that technical scheme can be modified or equivalent, and
Spirit and scope without departing from technical solution of the present invention.
Claims (6)
1. the preparation method of an anode material for lithium-ion batteries, it is characterised in that comprise the following steps:
(1) existing anode material for lithium-ion batteries A is synthesized in conventional manner；
(2) anode material for lithium-ion batteries A and solvent S is configured to slurry, under conditions of being stirred continuously
It is gradually added into rubbing of aluminum and anode material for lithium-ion batteries A in aluminum salt solution or colloidal sol, aluminum salt solution or colloidal sol
Your ratio is 0.002～0.02；
(3) mixed liquor of step (2) was dried through 4～24 hours in 70～100 DEG C after filtering, sieves,
Powder at 300～600 DEG C in air or oxygen atmosphere roasting 4～8 hours, obtain through sieving after natural cooling
Outer surface is coated with the anode material for lithium-ion batteries of alumina layer B；
(4) anode material for lithium-ion batteries that outer surface is coated with alumina layer B is configured to deionized water
Mixed liquor, whipping process adds organic carbon source in mixed liquor, is stirred until homogeneous mixing；
(5) by step (4) gained mixed liquor by obtaining at alumina layer B appearance bread after being spray-dried
Covering the lithium ion battery positive material powder of organic carbon, the inlet temperature of spray drying is 100～200 DEG C, outlet
Temperature is 50～80 DEG C；
(6) powder step (5) obtained loads crucible and is placed in tube furnace, and evacuation, by lazy
Property atmosphere, under inert atmosphere conditions heating 600～800 DEG C of roastings 0.5～2h, obtain through sieving after natural cooling
Outer surface is coated with alumina layer B and the anode material for lithium-ion batteries of carbon-coating C successively；
In described step (2), the addition speed of aluminum salt solution or colloidal sol is 1～20ml/min；Described step (2)
After being gradually added into aluminum salt solution or colloidal sol under conditions of being stirred continuously, continue stirring 1～4 hour, stirring speed
Degree is 200～2000r/min；
Described step (4) outer surface is coated with anode material for lithium-ion batteries and the deionization of alumina layer B
The mass ratio of water is 0.5:1～2.5:1；
The quality of the organic carbon source added in described step (4) be outer surface be coated with the lithium of alumina layer B from
The 2～20% of sub-cell positive material quality.
2. the preparation method of anode material for lithium-ion batteries as claimed in claim 1, it is characterised in that described
Solvent S in step (2) be water and can the mixture of organic solvent miscible with water, described organic solvent with
The weight ratio of water is 0～100；The mass ratio of described anode material for lithium-ion batteries A and solvent S is 0.5:1～5:1.
3. the preparation method of anode material for lithium-ion batteries as claimed in claim 1, it is characterised in that institute
Stating the weight concentration of aluminum salt solution or colloidal sol in step (2) is 10～50%, in described aluminum salt solution or colloidal sol,
Solvent be water or can organic solvent miscible with water or water and can be miscible with water the mixed liquor of organic solvent.
4. the preparation method of anode material for lithium-ion batteries as claimed in claim 2 or claim 3, it is characterised in that
Described organic solvent is alcohols or ketones solvent.
5. the preparation method of the anode material for lithium-ion batteries as described in claim 1 or 3, it is characterised in that
In the aluminum salt solution of described step (2) or colloidal sol, aluminium salt is at least one in an aluminium acetate, oxalic acid aluminum.
6. use the anode material for lithium-ion batteries that method as described in claim 1-5 is arbitrary prepares,
It is characterized in that, including existing anode material for lithium-ion batteries A, be coated on described lithium ion cell positive material
The alumina layer B and the carbon-coating C being coated on described alumina layer outer surface of material outer surface.
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| CN104009209A (en) * | 2014-06-05 | 2014-08-27 | 湖南工程学院 | Method for preparing lithium ion battery anode material with core-shell structure |
| US20170279109A1 (en) * | 2014-08-27 | 2017-09-28 | Nivo Systems, Inc. | Lithium metal oxide composites, and methods for preparing and using thereof |
| KR101791744B1 (en) * | 2014-09-30 | 2017-10-30 | 주식회사 엘지화학 | Cathode active material and preparation method thereof |
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| CN106025214B (en) * | 2016-06-07 | 2019-05-24 | 山东齐星新材料科技有限公司 | The aftertreatment technology of alumina-coated cobalt acid lithium |
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