CN107845786A - A kind of hud typed positive electrode, its preparation method and the purposes in lithium ion battery of composite cladding - Google Patents
A kind of hud typed positive electrode, its preparation method and the purposes in lithium ion battery of composite cladding Download PDFInfo
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- CN107845786A CN107845786A CN201710889122.4A CN201710889122A CN107845786A CN 107845786 A CN107845786 A CN 107845786A CN 201710889122 A CN201710889122 A CN 201710889122A CN 107845786 A CN107845786 A CN 107845786A
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- 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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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses hud typed positive electrode, its preparation method and the purposes in lithium ion battery of a kind of composite cladding.Described hud typed positive electrode includes the kernel that composite oxides clad anode material is formed, and is coated on the network combined beyond the region of objective existence shell of three-dimensional manometer of core surface.Methods described includes：First positive electrode material precursor is mixed with the precursor sol of composite oxides and disperseed, and adds a certain amount of polyethylene glycol, simultaneously pyroreaction is mixed after spray drying with lithium source, obtains the kernel of composite oxides clad anode material formation；Then the network combined beyond the region of objective existence shell of three-dimensional manometer is coated in the core surface, obtains target material.The preparation method of the present invention is simple, energy consumption is low, the hud typed positive electrode being prepared has excellent performance, using the hud typed positive electrode as the lithium ion battery prepared by the positive electrode active materials of lithium ion battery, it is more excellent with higher electric conductivity and cyclical stability, comprehensive electrochemical.
Description
Technical field
The invention belongs to new energy materialses field, be related to a kind of hud typed positive electrode of composite cladding, its preparation
Method and purposes, more particularly to hud typed positive electrode, its preparation method and in lithium ion battery of a kind of composite cladding
Purposes.
Background technology
The energy storage technologies economic heath national to one and national defense construction are most important.Lithium ion battery is because having energy
Amount and power density height, long lifespan, memory-less effect and it is environment-friendly outstanding advantages of by extensive concern, and rapidly sent out
Exhibition.In recent years, lithium ion battery is in hybrid vehicle (HEV), plug-in hybrid-power automobile and all-electric automobile (EV)
The strong interest of people is caused Deng the application in new-energy automobile.Lithium ion battery is soul and the new-energy automobile of electric car
Commercialization is crucial, and the positive electrode for accounting for cost 35% is not only to determine the key of performance of lithium ion battery, is even more its update
Core technology.On 2 20th, 2017, national four ministries and commissions existed《Promote automobile power cell industry development action scheme》Middle finger
Go out, lithium-ion-power cell monomer will respectively reach 300Wh/kg and 500Wh/kg than energy to the year two thousand twenty and 2015.In order to
Above-mentioned target is realized, nickel cobalt lithium aluminate cathode material is because having the advantages that high specific energy, long-life, it has also become research and development weight at this stage
Point, and the Commercialization application stage will be progressed into, there is boundless application prospect.But nickel cobalt lithium aluminate positive pole at present
Material still suffers from two prominent problems in use：(1) in charging process, due to Ni2+And Li+Radius it is very close,
Part Ni2+Li can be occupied+Room, ion mixing occurs, causes the irreversible capacity loss of material；(2) Ni in material exists
In Ni3+Or Ni4+High oxidation state when with very strong unstability, high temperature or high pressure can be by nickel cobalt aluminic acids under the conditions of overcharging
Lithium and the electrolyte oxidation at electrolyte interface, so as to be transformed into Ni2+, cause material structure to change, oxygen evolution occur and shows
As causing the penalty and capacity attenuation of nickel cobalt lithium aluminate cathode material.Meanwhile nickel cobalt lithium aluminate and electrolyte directly contact
The inert layers such as chemical reaction generation NiO easily occur, increase interface impedance, and then produce more heats to cause potential safety hazard.Especially
It is under more than 4.2V high voltages, and above-mentioned phenomenon is more prominent, significantly limit its reality in all kinds of electric automobiles
Using.
In order to overcome drawbacks described above, domestic and international researcher has carried out substantial amounts of research work.Such as, Hyeonjin Kimd etc.
Using liquid phase method in one layer of ammonium fluoride (NH of nickel cobalt lithium aluminate Surface coating4FHF), Li material surface to be dissociated2CO3And LiOH
Stable LiF is changed into, while the chemical property of no reduction nickel cobalt lithium aluminate, considerably reduces its pH value, and
And reduce the side reaction between material surface and electrolyte (Hyeonjin Kim, Kanghyeon Lee, Subeen Kim,
Yongseon Kim.Fluorination of free lithium residues on the surface of lithium
nickel cobalt aluminum oxide cathode materials for lithium ion
batteries.Materials and Design,2016,100:175-179.).Heidy Visbal etc. are using CVD in nickel
Cobalt lithium aluminate material surface is prepared for the thick DLC carbon material clads of 4nm, and research shows, nickel cobalt aluminium can be prevented after cladding
Side reaction between sour lithium and electrolyte, reduces interface resistance therebetween, has good cyclical stability and forthright again
Can (Heidy Visbal, Yuichi Aihara, Seitaro Ito, Taku Watanabe, Youngsin Park,
Seokgwang Doo.The effect of diamond-like carbon coating on
LiNi0.815Co0.15Al0.035O2particles for all solid-state lithium-ion batteries based
on Li2S-P2S5glass-ceramics.Journal of Power Sources,2016,314:85-92.).Nankai University
Pengfei Zhou etc. cladding process is dried in unformed SiO thick nickel cobalt lithium aluminate Surface coating 50nm by a step2, research
Show, coat 0.2wt%SiO2Nickel cobalt aluminic acid lithium material there is more preferable cycle performance, high rate performance and heat endurance, room
The specific capacity of 1C multiplying powers is up to 181.3mAh/g when warm, and capability retention is 90.7% after the circle of circulation 50.Due to coated Si O2Afterwards
The side reaction between nickel cobalt lithium aluminate and electrolyte is inhibited, reduces the resistance of SEI films, and then enhances nickel cobalt lithium aluminate knot
Structure and cyclical stability (Pengfei Zhou, Zhen Zhang, Huanju Meng, Yanying Lu, Jun Cao, Fangyi
Cheng,Zhanliang Tao,Jun Chen.SiO2-coated LiNi0.915Co0.075Al0.01O2cathode material
for rechargeable Li-ion batteries.Nanoscale,2016,8:19263.).Chinese invention patent is " a kind of
Coat the preparation method of spherical nickel-cobalt aluminium presoma, the preparation method of nickel cobalt lithium aluminate pole piece material " (number of patent application
201610803607.2) method using a kind of oxide cladding nickel cobalt lithium aluminate in Co or Mn, is disclosed, metal will be coated
Ion salt solution, complexing agent aqueous solution and the precipitating reagent aqueous solution are continuously injected into nickel cobalt aluminium hydroxide co-precipitation precursor slurries
In, it is 8.5-12.5 to control pH value of reaction system, obtains coating spherical nickel-cobalt aluminium presoma.Chinese invention patent " nickel cobalt aluminic acid
Lithium composite material and its preparation method and application " (number of patent application 201510292977.X), disclose a kind of nickel cobalt lithium aluminate
Composite, the material are made up of the LiFePO 4 material for being coated on nickel cobalt lithium aluminate surface, pass through polytetrafluoroethyl-ne therebetween
Alkene is bonded together, and can solve the problems, such as the flatulence of material.
Above-mentioned method for coating, e.g., (1) fluoride and Phosphate coating：Reduce electrolyte to inhibit the burn into of material
The side reaction of material and electrolyte, but simultaneously because its electrochemicaUy inert, it is also possible to the conduction to electronics and Li+ causes to hinder；
(2) carbon material coats：While protection materials itself, improve the electric conductivity of material, can be lifted material circulation and times
Rate performance.But, on the one hand, it is generally necessary to be pyrolyzed at high temperature by organic matter to realize carbon coating, and LNCA is being just under high temperature
The carbon reduction that pole material is easily generated；(3) oxide coats：Oxide surface cladding can form one layer of protection in material surface
Film, reduce corrosion of the electrolyte to material, prevent the side reaction between material and electrolyte and promote charge-conduction, be to improve just
The cyclicity of pole material, again forthright and heat endurance effective ways.But due to its electrochemicaUy inert, if oxide system
When selecting improper and clad blocked up, electronics and Li equally can be also hindered+Conduction.
In summary, if solving the irreversible capacity loss of nickel-cobalt lithium manganate cathode material, electrochemistry caused by oxygen evolution
Penalty and capacity fade problem are, it is necessary to from the mechanism and essential problem for causing the above-mentioned performance degradation of material, using conjunction
Suitable method for coating, suitable covering material is selected to solve the above problems.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of core of composite cladding
Shell mould positive electrode, its preparation method and the purposes in lithium ion battery.The present invention passes through composite oxides clad anode material
The kernel of formation, and be coated on outside the network combined beyond the region of objective existence shell coordinated of three-dimensional manometer, reached improvement electric conductivity, times
The forthright and excellent effect of cycle performance.The hud typed positive electrode coated using the composite of the present invention is as lithium-ion electric
Lithium ion battery prepared by the positive electrode active materials in pond, reversible discharge specific capacity is more than under 400mA/g current density
175mAh/g, capability retention is more than 85% after being circulated 200 times with 2C rate charge-discharge.
For the above-mentioned purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of hud typed positive electrode of composite cladding, the hud typed positive pole material
Material includes the kernel that composite oxides clad anode material is formed, and is coated on the three-dimensional manometer network of the core surface and answers
Compound shell.
In the hud typed positive electrode of the present invention, in the table for the kernel that the positive electrode by composite oxides cladding is formed
Bread covers the network combined beyond the region of objective existence shell of three-dimensional manometer, you can obtains target material --- the hud typed positive pole material of composite cladding
Material.The cladding of the shell does not need high-temperature burning process, both reduces energy consumption, but significantly enhance target material electric conductivity,
High rate performance and cyclical stability, the hud typed positive electrode of high performance composite cladding is obtained, there is novelty.
Currently preferred technical scheme is used as below, but not as the limitation to technical scheme provided by the invention, is led to
Following preferable technical scheme is crossed, can preferably reach and realize the technical purpose and beneficial effect of the present invention.
Preferably, counted using the gross mass of the hud typed positive electrode as 100%, composite oxides and three-dimensional in kernel
The gross mass percentage composition of nanometer network complex shell be 0.01~5%, such as 0.01%, 0.05%, 0.1%, 0.5%,
0.8%th, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 4.7% or 5% etc..
Preferably, the average grain diameter of the kernel be 5~20 μm, such as 5 μm, 7 μm, 8 μm, 10 μm, 12.5 μm, 15 μm,
16 μm, 17 μm, 18 μm or 20 μm etc..
Preferably, the positive electrode in kernel is nickel cobalt lithium aluminate.The hud typed positive electrode of the present invention is especially suitable for solution
Certainly irreversible capacity loss present in the application of nickel cobalt lithium aluminate, chemical property caused by oxygen evolution deteriorates and capacity attenuation is asked
Topic.
Preferably, the kernel is formed by the composite oxides cladding nickel cobalt lithium aluminate of cerium, titanium and zirconium, the kernel
Structural formula be LiNixCoyAlzMO2, 0.45≤x ＜ 1,0≤y≤0.35,0≤z ＜ 0.2；M=CeαTiβZrγ, 0 ＜ α ＜
The ＜ γ ＜ 0.2 of 0.2,0 ＜ β ＜ 0.2,0, and 0 ＜ alpha+betas+γ≤0.2.This optimal technical scheme use with storage oxygen function cerium,
The composite oxides of titanium and zirconium coat nickel cobalt lithium aluminate, to suppress the high pressure deoxidation phenomenon of nickel-cobalt lithium manganate cathode material, solve
The safety problem of the capacity attenuation and heat endurance difference of nickel-cobalt lithium manganate cathode material material in high pressure and under the conditions of overcharging, tool
There is novelty.
Preferably, the average thickness of the network combined beyond the region of objective existence shell of the three-dimensional manometer is 0.1~3 μm, such as 0.1 μm, 0.3 μ
M, 0.5 μm, 0.7 μm, 1 μm, 1.3 μm, 1.6 μm, 2 μm, 2.2 μm, 2.4 μm, 2.6 μm, 2.8 μm or 3 μm etc..
As the optimal technical scheme of hud typed positive electrode of the present invention, the network combined beyond the region of objective existence shell of three-dimensional manometer
For conducting polymer and the compound of conductive carbon material.Electro-chemical activity height, environmental stability are introduced in this optimal technical scheme
Conducting polymer good, electrical conductivity is high, carried out on the surface of the kernel formed by composite oxides clad anode material in situ
Polymerization cladding, the design can effectively solve positive electrode (such as nickel cobalt lithium aluminate) surface three dimension Specific surface area cladding not
, tap density is low, outstanding problem of poorly conductive, not only realizes conductive agent in the equal of nickel cobalt lithium aluminate cathode material surface
Even distribution, but also be used cooperatively with carbon material, collaboration improves the multiple mesh such as its electric conductivity, high rate performance and cyclical stability
's.
Preferably, the conducting polymer be polypyrrole, polyaniline, polythiophene or polyoxyethylene in any one or extremely
Few two kinds of mixture, or, the copolymer of any one or at least two above-mentioned polymer monomers.
Preferably, counted using the gross mass of the network combined beyond the region of objective existence shell of the three-dimensional manometer as 100%, the conducting polymer
Weight/mass percentage composition be 45~99.99%, such as 45%, 46%, 48%, 50%, 52%, 55%, 60%, 62.5%, 65%,
70%th, 73%, 76%, 80%, 82%, 84%, 87%, 90%, 92%, 93.5%, 95%, 97%, 98% or 99% etc..
It is highly preferred that the network combined beyond the region of objective existence shell of three-dimensional manometer is answering for conducting polymer, graphene and CNT
Compound.Conducting polymer and graphene and CNT are preferably formed three-dimensional manometer network structure, this group of distribution by the present invention
Close and architectural characteristic, make that collaboration improves being evenly coated property, tap density, electric conductivity, forthright and cycle performance effect reaches again
Most preferably.
Preferably, the CNT is any one in single-walled carbon nanotube or multi-walled carbon nanotube or at least two
Mixture, preferably multi-walled carbon nanotube.
Preferably, the CNT is the CNT of acidified processing.
Preferably, counted using the gross mass of the network combined beyond the region of objective existence shell of the three-dimensional manometer as 100%, the graphene and carbon are received
The gross mass percentage composition of mitron be 0.01~55%, such as 0.01%, 0.05%, 0.1%, 0.2%, 0.5%, 1%,
1.5%th, 2.5%, 4%, 5%, 7%, 10%, 15%, 20%, 22.5%, 25%, 30%, 33%, 36%, 40%, 45%,
50%th, 52% or 55% etc..
Preferably, the mass ratio of the graphene and CNT is m, and 0 ＜ m ＜ 1, for example, 0.2,0.3,0.4,0.5,
0.6th, 0.7,0.8 or 0.9 etc..
As the further preferred technical scheme of hud typed positive electrode of the present invention, the hud typed positive electrode bag
Include the kernel that the composite oxides cladding nickel cobalt lithium aluminate of cerium, titanium and zirconium is formed, and be coated on the core surface by leading
The network combined beyond the region of objective existence shell of three-dimensional manometer that electric polymer, graphene and CNT are formed, wherein, the average grain diameter of kernel is 5
~20 μm, the average thickness of shell is 0.1~3 μm, and the gross mass of composite oxides and shell in kernel accounts for hud typed positive pole
The 0.01~5% of material.
In this optimal technical scheme, the compound of cerium oxide, titanium oxide and zirconium oxide can absorb electrode material in charge and discharge
The release oxygen inside nickel cobalt lithium aluminate cathode material occurred when being used under electric process, especially condition of high voltage, on the other hand, is adopted
With conducting polymer, graphene and CNT with the use of in-stiu coating is carried out, can make full use of：Native electronic electric conductivity
High conductivity, high stability and the good positive electrode activity of conducting polymer such as polypyrrole；The high conductivity of graphene with
And can be Li+The characteristic of good transmission channel is provided；High conductivity, bigger serface and the good storage lithium of CNT are special
Property；Above-mentioned substance is effectively combined, both can improve nickel cobalt lithium aluminate positive pole material by introducing conducting polymer such as polypyrrole
The electrical conductivity of material, a small amount of graphene, CNT and traditional carbon material can effectively be combined again, realize various storerooms
Have complementary advantages, improve tap density, electrical conductivity and the cyclical stability of nickel cobalt lithium aluminate cathode material.
Second aspect, the present invention provide the preparation of the hud typed positive electrode of composite cladding as described in relation to the first aspect
Method, it the described method comprises the following steps：
A, first, positive electrode material precursor is mixed with the precursor sol of composite oxides and disperseed, and divided to what is obtained
The polyethylene glycol of weight/mass percentage composition 0.1~0.5% is added in dispersion liquid, is mixed after spray drying with lithium source and to carry out high temperature anti-
Should, obtain the kernel of composite oxides clad anode material formation；
B, then, the network combined beyond the region of objective existence shell of three-dimensional manometer is coated in the core surface, obtains the core of composite cladding
Shell mould positive electrode.
In the method for the present invention, using the oxygen that the covering material cerium of oxygen, titanium and zirconium can be discharged effectively inside absorbing material
Compound carries out in-stiu coating, forms inner nuclear material, then coats one layer of three-dimensional manometer network structure in its in situ Polymerization again
Complex shell, pass through the final target material for obtaining the present invention of above-mentioned two class cladding --- composite coats hud typed
Positive electrode, the problem of can effectively solve the problem that positive electrode performance degradation.
As the optimal technical scheme of the method for the invention, positive electrode material precursor described in step a is nickel cobalt aluminium forerunner
Any one in body or nickel cobalt manganese presoma, preferably nickel cobalt aluminium presoma, the carbonate precursor of further preferred nickel cobalt aluminium
Or the hydroxide precursor of nickel cobalt aluminium.
Preferably, the precursor sol of composite oxides described in step a by each metal in composite oxides hydrolysis of alkoxide
After obtain.
Preferably, the precursor sol of composite oxides described in step a be cerium, titanium and zirconium mixed sols, by cerium, titanium and
Obtained after the hydrolysis of alkoxide of zirconium.
Preferably, lithium source described in step a includes lithium chloride, lithium bromide, lithium phosphate, lithium dihydrogen phosphate, the lithium of phosphoric acid hydrogen two, sulphur
Sour lithium, lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, lithium benzoate or lithium citrate
In any one or at least two combination, preferably lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, formic acid
In lithium, lithium citrate or tert-butyl alcohol lithium any one or at least two combination, more preferably lithium carbonate, hydroxide
In lithium, lithium acetate or lithium oxalate any one or at least two combination.
Preferably, pyroreaction described in step a is：Under oxygen atmosphere, 350~650 DEG C of the first temperature is first warming up to
Insulation, then it is warming up to 650~950 DEG C of second temperature insulation.
In this optimal technical scheme, the first temperature be 350~650 DEG C, such as 350 DEG C, 375 DEG C, 400 DEG C, 450 DEG C, 500
DEG C, 520 DEG C, 550 DEG C, 575 DEG C, 600 DEG C or 650 DEG C etc..
In this optimal technical scheme, second temperature be 650~950 DEG C, such as 650 DEG C, 700 DEG C, 720 DEG C, 750 DEG C, 775
DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 925 DEG C or 950 DEG C etc..
Preferably, the heating rate for being warming up to first temperature is 1~10 DEG C/min, for example, 1 DEG C/min, 3 DEG C/min,
5 DEG C/min, 6 DEG C/min, 8 DEG C/min or 10 DEG C/min etc..
Preferably, in the time of first temperature be 2~20h, for example, 2h, 4h, 5h, 6.5h, 8h, 10h, 12h,
15h, 17.5h, 18.5h or 20h etc..
Preferably, the heating rate for being warming up to the second temperature is 1~10 DEG C/min, for example, 1 DEG C/min, 3 DEG C/min,
5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min or 10 DEG C/min etc..
Preferably, be 2~24h in the time of second temperature insulation, for example, 2h, 4h, 6h, 7h, 8h, 10h, 12h,
15h, 16h, 18h, 20h, 22h or 24h etc..
As the optimal technical scheme of the method for the invention, cladding is in-stiu coating described in step b.
Preferably, the network combined beyond the region of objective existence shell of three-dimensional manometer described in step b is the compound of conducting polymer and conductive carbon material
The compound of thing, preferably conducting polymer, graphene and CNT.
Preferably, the CNT is the CNT after acidification, is the step of the acidification：Carbon is received
Mitron is 3 in volume ratio:In room temperature ultrasonic disperse 3h in 1 concentrated sulfuric acid and concentrated nitric acid, then in 60 DEG C of speed with 800r/min
Degree stirring 5h, after being cooled to room temperature, is poured slowly into the mixture of ice and water of deionized water, filters, washed extremely through cellulose ester membrane
Neutrality, obtain the CNT after acidification.
As the optimal technical scheme of the method for the invention, step b is：In the core surface in-stiu coating by polymerizeing
The network combined beyond the region of objective existence shell of three-dimensional manometer that thing, graphene and CNT are formed, specifically includes following steps：
1. adding surfactant into graphene oxide, disperse, then add hydrazine hydrate, product is separated except unnecessary
Surfactant, obtain between graphene layer formed micella reduced graphene；
2. the product after step 1. middle separation is scattered in a solvent and ultrasonic, then add what step a was obtained thereto
Kernel, continue ultrasonic disperse；
3. adding conducting polymer or monomer into the step 2. product of ultrasonic disperse, continue ultrasound, add persulfuric acid
Ammonium and CNT, stirring progress polymerisation, product are dried after separation, obtained in core surface by polymerizeing in ice-water bath
The network combined beyond the region of objective existence shell of three-dimensional manometer that thing, graphene and CNT are formed.
In this optimal technical scheme, 1. the graphene oxide is scattered graphene oxide to step.
In this optimal technical scheme, 1. it is committed step that step adds surfactant, in graphene oxide by hydrazine hydrate
Surfactant forms micella between graphene layer during reduction.
Preferably, 1. the surfactant is cetyl trimethylammonium bromide, cetyl trimethyl chlorination to step
In ammonium, lauryl sodium sulfate or neopelex any one or at least two mixture.
Preferably, step is 1. described disperses to carry out through ultrasonic wave.
Preferably, 2. the solvent is in the chloroformic solution of ethanol, deionized water, inorganic proton acid or ferric trichloride to step
Any one or at least two mixture.
Preferably, 2. the time for continuing ultrasonic disperse is 0.5~1h to step, for example, 0.5h, 0.6h, 0.7h, 0.8h,
0.9h or 1h etc..
Preferably, 3. the time for continuing ultrasound is 30~60min to step, for example, 30min, 35min, 40min,
45min, 50min or 60min etc..
Preferably, the time of the step 3. polymerisation is 18~24h, for example, 18h, 18.5h, 19h, 20h, 20.5h,
21h, 22h, 22.5h, 23h, 23.5h or 24h etc..
Preferably, step 3. the drying temperature be 40~80 DEG C, such as 40 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 75
DEG C or 89 DEG C etc..
Preferably, 3. the drying is 60 DEG C of vacuum drying to step.
The third aspect, the present invention provide a kind of lithium ion battery, and the lithium ion battery includes answering described in first aspect
The hud typed positive electrode of condensation material cladding.
Lithium ion battery using the hud typed positive electrode of composite of the present invention cladding has height ratio capacity, height
Outstanding advantages of cyclical stability and forthright high power, comprehensive electrochemical is more excellent.It is reversible under 400mA/g current density
Specific discharge capacity is more than 175mAh/g, and capability retention is more than 85% after being circulated 200 times with 2C rate charge-discharge.
Compared with the prior art, the present invention has the advantages that：
(1) the application uses the combined oxidation cladding nickel cobalt lithium aluminate cathode material of the cerium with storage oxygen function, titanium, zirconium,
To suppress the high pressure deoxidation phenomenon of nickel cobalt lithium aluminate cathode material, solve nickel cobalt lithium aluminate cathode material material in high pressure and overcharge
Under the conditions of capacity attenuation and heat endurance difference safety problem, have novelty.
(2) existed using three-dimensional manometer multi-layered network structural conductive conducting polymer/graphene/carbon nano-tube/composite
In-situ polymerization cladding is carried out by the nickel cobalt lithium aluminate cathode material surface of cerium, titanium, zirconium in-stiu coating, you can obtains target material
The nickel cobalt lithium aluminate cathode material of material-composite cladding, it is not necessary to high-temperature burning process, energy consumption is both reduced, and significantly
Electric conductivity, high rate performance and the cyclical stability of target material are enhanced, obtains the nickel cobalt aluminium of high performance composite cladding
Sour lithium anode material, there is novelty.
(3) electro-chemical activity height, the conducting polymer that environmental stability is good, electrical conductivity is high are introduced, by cerium, titanium, zirconium
The nickel cobalt lithium aluminate cathode material surface of in-stiu coating carries out in-situ polymerization cladding, and the design can effectively solve nickel cobalt lithium aluminate just
Pole material surface three-dimensional manometer network structure cladding is uneven, tap density is low, poorly conductive outstanding problem, not only realizes and leads
Electric agent is uniformly distributed nickel cobalt lithium aluminate cathode material surface, and it is multiple to improve its electric conductivity and cyclical stability etc. again
Purpose.
(4) preparation method provided by the invention is simple, and energy consumption is low, has boundless actual application prospect.
(5) positive-active material of the hud typed positive electrode coated using the composite of the present invention as lithium ion battery
The prepared lithium ion battery of material, has higher electric conductivity and cyclical stability, and comprehensive electrochemical is more excellent.
Reversible discharge specific capacity is more than 175mAh/g under 400mA/g current density, capacity after being circulated 200 times with 2C rate charge-discharge
Conservation rate is more than 85%.
Embodiment
Technical scheme is further illustrated below by embodiment.
Used CNT is the CNT after acidification in following embodiments, and its acidification step is：By carbon
Nanotube is 3 in volume ratio:Ultrasonic disperse 3h at room temperature in 1 concentrated sulfuric acid and concentrated nitric acid, then in 60 DEG C with 800r/min's
Speed stirs 5h, after being cooled to room temperature, is poured slowly into the mixture of ice and water of deionized water, filters, washs through cellulose ester membrane
To neutrality, the CNT after acidification is obtained.
Embodiment 1
(1) the nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium is prepared：
According to chemical formula LiNi0.45Al0.18Ce0.2Ti0.1Zr0.07O2Dispensing is weighed, by the hydroxide precursor of nickel cobalt aluminium
It is dispersed and to dispersion liquid with the mixed sols (mixed sols after the hydrolysis of alkoxide of cerium, titanium and zirconium from obtaining) of cerium, titanium, zirconium
It is middle to add the polyethylene glycol that weight/mass percentage composition is 0.1%, uniformly mixed with lithium hydroxide after spray drying, and in oxygen atmosphere
Under with 1 DEG C/min heating rates from room temperature to 350 DEG C, constant temperature 20h, then with same heating rate rise to 650 DEG C, constant temperature
Room temperature is cooled to after 24h, obtains the nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium, i.e.,
For kernel.
(2) material M1 surface in situ coat one layer by conducting polymer, graphene and CNT it is compound obtain three
Specific surface area composite B is tieed up as shell, obtains an object of the application material --- the nickel cobalt aluminium of composite cladding
Sour lithium anode material.Specifically method for coating is：
1. adding cetyl trimethylammonium bromide into scattered graphene oxide, disperse, then add hydrazine hydrate,
Surfactant is formed micella between graphene layer during graphene oxide is by hydrazine hydrate reduction, product is separated
Except unnecessary surfactant, the reduced graphene of the formation micella between graphene layer is obtained；
2. the product after step 1. middle separation is scattered in a solvent and ultrasonic, institute in step (1) is then added thereto
The nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium stated, continue ultrasonic disperse 0.5h；
3. to above-mentioned steps 2. middle addition aniline monomer, continue ultrasonic 30min, add ammonium persulfate and CNT,
Stirring carries out polymerisation 18h in ice-water bath, and product is dried to obtain after separation by conducting polymer, graphene and CNT
Compound obtained three-dimensional manometer network structure composite coats the target material of formation --- the nickel cobalt of composite cladding
Lithium aluminate cathode material.
Nickel cobalt lithium aluminate is being just after cladding for the gross mass of cerium, titanium, zirconium mixed oxide and composite B in the present embodiment
Shared weight/mass percentage composition is 0.01% in pole material (i.e. the nickel cobalt lithium aluminate cathode material of composite cladding), its
In, conductive polymer polyanaline weight/mass percentage composition shared in composite B is 45%；The matter of graphene and CNT
For amount than being 0.1, the gross mass percentage composition of graphene and CNT shared by composite B is 3%.
The nickel cobalt lithium aluminate cathode material of composite cladding prepared by the present embodiment, in 400mA/g current density
Lower reversible discharge specific capacity is 176mAh/g, and capability retention is 86% after being circulated 200 times using 2C rate charge-discharge.
Embodiment 2
(1) the nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium is prepared：
According to chemical formula LiNi0.9Co0.01Al0.04Ce0.02Ti0.02Zr0.03O2Dispensing is weighed, by the hydroxide of nickel cobalt aluminium
Presoma and cerium, titanium, the mixed sols (mixed sols after the hydrolysis of alkoxide of cerium, titanium and zirconium from obtaining) of zirconium it is dispersed and to
The polyethylene glycol that weight/mass percentage composition is 0.5% is added in dispersion liquid, is uniformly mixed with lithium carbonate after spray drying, and in oxygen
With 10 DEG C/min heating rates from room temperature to 650 DEG C, constant temperature 2h under atmosphere, then with same heating rate 950 DEG C are risen to,
Room temperature is cooled to after constant temperature 2h, obtains the nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium,
As kernel.
(2) material M1 surface in situ coat one layer by conducting polymer, graphene and CNT it is compound obtain three
Specific surface area composite B is tieed up as shell, obtains an object of the application material --- the nickel cobalt aluminium of composite cladding
Sour lithium anode material.Specifically method for coating is：
1. adding cetyl trimethylammonium bromide into scattered graphene oxide, disperse, then add hydrazine hydrate,
Surfactant is formed micella between graphene layer during graphene oxide is by hydrazine hydrate reduction, product is separated
Except unnecessary surfactant, the reduced graphene of the formation micella between graphene layer is obtained；
2. the product after step 1. middle separation is scattered in a solvent and ultrasonic, institute in step (1) is then added thereto
The nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium stated, continue ultrasonic disperse 1h；
3. to above-mentioned steps 2. middle addition thiophene monomer, continue ultrasonic 60min, add ammonium persulfate and CNT,
Stirring carries out polymerisation 24h in ice-water bath, and product is dried to obtain after separation by conducting polymer, graphene and CNT
Compound obtained three-dimensional manometer network structure composite coats the target material of formation --- the nickel cobalt of composite cladding
Lithium aluminate cathode material.
Nickel cobalt lithium aluminate is being just after cladding for the gross weight of cerium, titanium, zirconium mixed oxide and composite B in the present embodiment
Shared weight/mass percentage composition is respectively 0.1% He in pole material (i.e. the nickel cobalt lithium aluminate cathode material of composite cladding)
5%, wherein, conductive polymer polyanaline weight/mass percentage composition shared in composite B is 99.99%；Graphene and carbon
The mass ratio of nanotube is 0.3, and the gross mass percentage composition of graphene and CNT shared by composite B is
0.01%.
The nickel cobalt lithium aluminate cathode material of composite cladding prepared by the present embodiment, in 400mA/g current density
Lower reversible discharge specific capacity is 178mAh/g, and capability retention is 87% after being circulated 200 times using 2C rate charge-discharge.
Embodiment 3
(1) the nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium is prepared
According to chemical formula LiNi0.6Co0.05Al0.1Ce0.1Ti0.15Zr0.05O2Dispensing is weighed, by the carbonic acid salt precursor of nickel cobalt aluminium
Body and cerium, titanium, the mixed sols (mixed sols after the hydrolysis of alkoxide of cerium, titanium and zirconium from obtaining) of zirconium are dispersed and to scattered
The polyethylene glycol that weight/mass percentage composition is 0.2% is added in liquid, is uniformly mixed with lithium nitrate after spray drying, and in oxygen atmosphere
Under with 3 DEG C/min heating rates from room temperature to 400 DEG C, constant temperature 16h, then with same heating rate rise to 700 DEG C, constant temperature
Room temperature is cooled to after 8h, obtains the nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium, is
Kernel.
(2) material M1 surface in situ coat one layer by conducting polymer, graphene and CNT it is compound obtain three
Specific surface area composite B is tieed up as shell, obtains an object of the application material --- the nickel cobalt aluminium of composite cladding
Sour lithium anode material.Specifically method for coating is：
1. adding hexadecyltrimethylammonium chloride into scattered graphene oxide, disperse, then add hydrazine hydrate,
Surfactant is formed micella between graphene layer during graphene oxide is by hydrazine hydrate reduction, product is separated
Except unnecessary surfactant, the reduced graphene of the formation micella between graphene layer is obtained；
2. the product after step 1. middle separation is scattered in a solvent and ultrasonic, institute in step (1) is then added thereto
The nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium stated, continue ultrasonic disperse 1h；
3. to above-mentioned steps 2. middle addition thiophene monomer, continue ultrasonic 40min, add ammonium persulfate and CNT,
Stirring carries out polymerisation 20h in ice-water bath, and product is dried to obtain after separation by conducting polymer, graphene and CNT
Compound obtained three-dimensional manometer network structure composite coats the target material of formation --- the nickel cobalt of composite cladding
Lithium aluminate cathode material.
Nickel cobalt lithium aluminate is being just after cladding for the gross weight of cerium, titanium, zirconium mixed oxide and composite B in the present embodiment
Shared weight/mass percentage composition is respectively 5% He in pole material (i.e. the nickel cobalt lithium aluminate cathode material of composite cladding)
0.1%, wherein, conductive polymer polyanaline weight/mass percentage composition shared in composite B is 50%；Graphene and carbon are received
The mass ratio of mitron is 0.5, and the gross mass percentage composition of graphene and CNT shared by composite B is 55%.
The nickel cobalt lithium aluminate cathode material of composite cladding prepared by the present embodiment, in 400mA/g current density
Lower reversible discharge specific capacity is 180mAh/g, and capability retention is 89% after being circulated 200 times using 2C rate charge-discharge.
Embodiment 4
(1) the nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium is prepared：
According to chemical formula LiNi0.7Co0.1Al0.05Ce0.05Ti0.5Zr0.5O2Dispensing is weighed, before the hydroxide of nickel cobalt aluminium
Drive body and cerium, titanium, the mixed sols (mixed sols after the hydrolysis of alkoxide of cerium, titanium and zirconium from obtaining) of zirconium it is dispersed and to point
The polyethylene glycol that weight/mass percentage composition is 0.3% is added in dispersion liquid, is uniformly mixed with acetoxylation lithium after spray drying, and in oxygen
With 7 DEG C/min heating rates from room temperature to 450 DEG C, constant temperature 14h under atmosphere, then with same heating rate 800 DEG C are risen to,
Room temperature is cooled to after constant temperature 12h, obtains the nickel cobalt lithium aluminate cathode material coated jointly by the composite oxides A of cerium, titanium, zirconium
M1, as kernel.
(2) material M1 surface in situ coat one layer by conducting polymer, graphene and CNT it is compound obtain three
Specific surface area composite B is tieed up as shell, obtains an object of the application material --- the nickel cobalt aluminium of composite cladding
Sour lithium anode material.Specifically method for coating is：
1. adding lauryl sodium sulfate into scattered graphene oxide, disperse, then add hydrazine hydrate, aoxidizing
Graphene is made surfactant form micella between graphene layer during hydrazine hydrate reduction, and product is separated except unnecessary
Surfactant, obtain between graphene layer formed micella reduced graphene；
2. the product after step 1. middle separation is scattered in a solvent and ultrasonic, institute in step (1) is then added thereto
The nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium stated, continue ultrasonic disperse 1h；
3. to above-mentioned steps 2. middle addition pyrrole monomer, continue ultrasonic 50min, add ammonium persulfate and CNT,
Stirring carries out polymerisation 22h in ice-water bath, and product is dried to obtain after separation by conducting polymer, graphene and CNT
Compound obtained three-dimensional manometer network structure composite coats the target material of formation --- the nickel cobalt of composite cladding
Lithium aluminate cathode material.
Nickel cobalt lithium aluminate is being just after cladding for the gross weight of cerium, titanium, zirconium mixed oxide and composite B in the present embodiment
Shared weight/mass percentage composition is respectively 0.5% He in pole material (i.e. the nickel cobalt lithium aluminate cathode material of composite cladding)
1%, wherein, conductive polymer polyanaline weight/mass percentage composition shared in composite B is 60%；Graphene and carbon nanometer
The mass ratio of pipe is 0.7, and the gross mass percentage composition of graphene and CNT shared by composite B is 0.5%.
The nickel cobalt lithium aluminate cathode material of composite cladding prepared by the present embodiment, in 400mA/g current density
Lower reversible discharge specific capacity is 190mAh/g, and capability retention is 86% after being circulated 200 times using 2C rate charge-discharge.
Embodiment 5
(1) the nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium is prepared：
According to chemical formula LiNi0.8Co0.15Al0.02Ce0.01Ti0.01Zr0.01O2Dispensing is weighed, before the carbonate of nickel cobalt aluminium
Drive body and cerium, titanium, the mixed sols (mixed sols after the hydrolysis of alkoxide of cerium, titanium and zirconium from obtaining) of zirconium it is dispersed and to point
The polyethylene glycol that weight/mass percentage composition is 0.4% is added in dispersion liquid, is uniformly mixed with lithium hydroxide after spray drying, and in oxygen
With 9 DEG C/min heating rates from room temperature to 500 DEG C, constant temperature 12h under atmosphere, then with same heating rate 850 DEG C are risen to,
Room temperature is cooled to after constant temperature 14h, obtains the nickel cobalt lithium aluminate cathode material coated jointly by the composite oxides A of cerium, titanium, zirconium
M1, as kernel.
(2) material M1 surface in situ coat one layer by conducting polymer, graphene and CNT it is compound obtain three
Specific surface area composite B is tieed up as shell, obtains an object of the application material --- the nickel cobalt aluminium of composite cladding
Sour lithium anode material.Specifically method for coating is：
1. adding neopelex into scattered graphene oxide, disperse, hydrazine hydrate is then added, in oxygen
Graphite alkene is made surfactant form micella between graphene layer during hydrazine hydrate reduction, and product is separated except more
Remaining surfactant, obtain being formed the reduced graphene of micella between graphene layer；
2. the product after step 1. middle separation is scattered in a solvent and ultrasonic, institute in step (1) is then added thereto
The nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium stated, continue ultrasonic disperse 1h；
3. adding thiophene monomer and polyoxyethylene to above-mentioned steps are 2. middle, continue ultrasonic 55min, add ammonium persulfate and carbon
Nanotube, stirring progress polymerisation 20h, product are dried to obtain after separation by conducting polymer, graphene in ice-water bath
Target material --- the composite of formation is coated with the compound obtained three-dimensional manometer network structure composite of CNT
The nickel cobalt lithium aluminate cathode material of cladding.
Nickel cobalt lithium aluminate is being just after cladding for the gross weight of cerium, titanium, zirconium mixed oxide and composite B in the present embodiment
Shared weight/mass percentage composition is respectively 1% and 3% in the pole material nickel cobalt lithium aluminate cathode material of cladding (i.e. composite),
Wherein, conductive polymer polyanaline weight/mass percentage composition shared in composite B is 70%；Graphene and CNT
Mass ratio is 0.9, and the gross mass percentage composition of graphene and CNT shared by composite B is 5%.
The nickel cobalt lithium aluminate cathode material of composite cladding prepared by the present embodiment, in 400mA/g current density
Lower reversible discharge specific capacity is 192mAh/g, and capability retention is 87% after being circulated 200 times using 2C rate charge-discharge.
Embodiment 6
(1) the nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium is prepared：
According to chemical formula LiNi0.5Co0.35Al0.1Ce0.03Ti0.01Zr0.01O2Dispensing is weighed, before the hydroxide of nickel cobalt aluminium
Drive body and cerium, titanium, the mixed sols (mixed sols after the hydrolysis of alkoxide of cerium, titanium and zirconium from obtaining) of zirconium it is dispersed and to point
The polyethylene glycol that weight/mass percentage composition is 0.15% is added in dispersion liquid, is uniformly mixed with carbonic acid dihydro lithium after spray drying, and
With 10 DEG C/min heating rates from room temperature to 550 DEG C, constant temperature 10h under oxygen atmosphere, then risen to same heating rate
900 DEG C, room temperature is cooled to after constant temperature 16h, obtains the nickel cobalt lithium aluminate positive pole coated jointly by the composite oxides A of cerium, titanium, zirconium
Material M1, as kernel.
(2) material M1 surface in situ coat one layer by conducting polymer, graphene and CNT it is compound obtain three
Specific surface area composite B is tieed up as shell, obtains an object of the application material --- the nickel cobalt aluminium of composite cladding
Sour lithium anode material.Specifically method for coating is：
1. adding neopelex into scattered graphene oxide, disperse, hydrazine hydrate is then added, in oxygen
Graphite alkene is made surfactant form micella between graphene layer during hydrazine hydrate reduction, and product is separated except more
Remaining surfactant, obtain being formed the reduced graphene of micella between graphene layer；
2. the product after step 1. middle separation is scattered in a solvent and ultrasonic, institute in step (1) is then added thereto
The nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium stated, continue ultrasonic disperse 1h；
3. to above-mentioned steps 2. middle addition aniline monomer, continue ultrasonic 45min, add ammonium persulfate and CNT,
Stirring carries out polymerisation 21h in ice-water bath, and product is dried to obtain after separation by conducting polymer, graphene and CNT
Compound obtained three-dimensional manometer network structure composite coats the target material of formation --- the nickel cobalt of composite cladding
Lithium aluminate cathode material.
Nickel cobalt lithium aluminate is being just after cladding for the gross weight of cerium, titanium, zirconium mixed oxide and composite B in the present embodiment
Shared weight/mass percentage composition is respectively 3% He in pole material (i.e. the nickel cobalt lithium aluminate cathode material of composite cladding)
0.5%, wherein, conductive polymer polyanaline weight/mass percentage composition shared in composite B is 80%；Graphene and carbon are received
The mass ratio of mitron is 0.2, and the gross mass percentage composition of graphene and CNT shared by composite B is 40%.
The nickel cobalt lithium aluminate cathode material of composite cladding prepared by the present embodiment, in 400mA/g current density
Lower reversible discharge specific capacity is 195mAh/g, and capability retention is 86% after being circulated 200 times using 2C rate charge-discharge.
Embodiment 7
(1) the nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium is prepared：
According to chemical formula LiNi0.55Co0.2Al0.15Ce0.04Ti0.03Zr0.03O2Dispensing is weighed, before the carbonate of nickel cobalt aluminium
Drive body and cerium, titanium, the mixed sols (mixed sols after the hydrolysis of alkoxide of cerium, titanium and zirconium from obtaining) of zirconium it is dispersed and to point
The polyethylene glycol that weight/mass percentage composition is 0.1% is added in dispersion liquid, is uniformly mixed with lithium hydroxide after spray drying, and in oxygen
With 2 DEG C/min heating rates from room temperature to 600 DEG C, constant temperature 8h under atmosphere, then with same heating rate 750 DEG C are risen to,
Room temperature is cooled to after constant temperature 10h, obtains the nickel cobalt lithium aluminate cathode material coated jointly by the composite oxides A of cerium, titanium, zirconium
M1, as kernel.
(2) material M1 surface in situ coat one layer by conducting polymer, graphene and CNT it is compound obtain three
Specific surface area composite B is tieed up as shell, obtains an object of the application material --- the nickel cobalt aluminium of composite cladding
Sour lithium anode material.Specifically method for coating is：
1. adding neopelex into scattered graphene oxide, disperse, hydrazine hydrate is then added, in oxygen
Graphite alkene is made surfactant form micella between graphene layer during hydrazine hydrate reduction, and product is separated except more
Remaining surfactant, obtain being formed the reduced graphene of micella between graphene layer；
2. the product after step 1. middle separation is scattered in a solvent and ultrasonic, institute in step (1) is then added thereto
The nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium stated, continue ultrasonic disperse 1h；
3. to above-mentioned steps 2. middle addition aniline monomer, continue ultrasonic 35min, add ammonium persulfate and CNT,
Stirring carries out polymerisation 23h in ice-water bath, and product is dried to obtain after separation by conducting polymer, graphene and CNT
Compound obtained three-dimensional manometer network structure composite coats the target material of formation --- the nickel cobalt of composite cladding
Lithium aluminate cathode material.
Nickel cobalt lithium aluminate is being just after cladding for the gross weight of cerium, titanium, zirconium mixed oxide and composite B in the present embodiment
Shared weight/mass percentage composition is respectively 0.3% He in pole material (i.e. the nickel cobalt lithium aluminate cathode material of composite cladding)
0.05%, wherein, conductive polymer polyanaline weight/mass percentage composition shared in composite B is 90%；Graphene and carbon
The mass ratio of nanotube is 0.4, and the gross mass percentage composition of graphene and CNT shared by composite B is 20%.
The nickel cobalt lithium aluminate cathode material of composite cladding prepared by the present embodiment, in 400mA/g current density
Lower reversible discharge specific capacity is 193mAh/g, and capability retention is 88% after being circulated 200 times using 2C rate charge-discharge.
Embodiment 8
(1) the nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium is prepared：
According to chemical formula LiNi0.65Co0.25Al0.03Ce0.03Ti0.04Zr0.01O2Dispensing is weighed, by the hydroxide of nickel cobalt aluminium
Presoma and cerium, titanium, the mixed sols (mixed sols after the hydrolysis of alkoxide of cerium, titanium and zirconium from obtaining) of zirconium it is dispersed and to
The polyethylene glycol that weight/mass percentage composition is 0.2% is added in dispersion liquid, is uniformly mixed with lithium carbonate after spray drying, and in oxygen
With 6 DEG C/min heating rates from room temperature to 520 DEG C, constant temperature 6h under atmosphere, then with same heating rate 720 DEG C are risen to,
Room temperature is cooled to after constant temperature 11h, obtains the nickel cobalt lithium aluminate cathode material coated jointly by the composite oxides A of cerium, titanium, zirconium
M1, as kernel.
(2) material M1 surface in situ coat one layer by conducting polymer, graphene and CNT it is compound obtain three
Specific surface area composite B is tieed up as shell, obtains an object of the application material --- the nickel cobalt aluminium of composite cladding
Sour lithium anode material.Specifically method for coating is：
1. adding neopelex into scattered graphene oxide, disperse, hydrazine hydrate is then added, in oxygen
Graphite alkene is made surfactant form micella between graphene layer during hydrazine hydrate reduction, and product is separated except more
Remaining surfactant, obtain being formed the reduced graphene of micella between graphene layer；
2. the product after step 1. middle separation is scattered in a solvent and ultrasonic, institute in step (1) is then added thereto
The nickel cobalt lithium aluminate cathode material M1 coated jointly by the composite oxides A of cerium, titanium, zirconium stated, continue ultrasonic disperse 1h；
3. adding thiophene monomer and aniline monomer to above-mentioned steps are 2. middle, continue ultrasonic 55min, add ammonium persulfate and carbon
Nanotube, stirring progress polymerisation 24h, product are dried to obtain after separation by conducting polymer, graphene in ice-water bath
Target material --- the composite of formation is coated with the compound obtained three-dimensional manometer network structure composite of CNT
The nickel cobalt lithium aluminate cathode material of cladding.
Nickel cobalt lithium aluminate is being just after cladding for the gross weight of cerium, titanium, zirconium mixed oxide and composite B in the present embodiment
Shared weight/mass percentage composition is respectively 2% He in pole material (i.e. the nickel cobalt lithium aluminate cathode material of composite cladding)
0.15%, wherein, conductive polymer polyanaline weight/mass percentage composition shared in composite B is 55%；Graphene and carbon
The mass ratio of nanotube is 0.6, and the gross mass percentage composition of graphene and CNT shared by composite B is 30%.
The nickel cobalt lithium aluminate cathode material of composite cladding prepared by the present embodiment, in 400mA/g current density
Lower reversible discharge specific capacity is 185mAh/g, and capability retention is 90% after being circulated 200 times using 2C rate charge-discharge.
Comparative example 1
In addition to the composite oxides A for not coating cerium, titanium and zirconium, other preparation methods and condition are same as Example 1.
The prepared nickel cobalt lithium aluminate cathode material of this contrast, the reversible discharge specific capacity under 400mA/g current density
For 165mAh/g, capability retention is 75% after being circulated 200 times using 2C rate charge-discharge.
Comparative example 2
Except not coating by conducting polymer, graphene and the compound obtained three-dimensional manometer network structure composite wood of CNT
Expect outside B, other preparation methods and condition are same as Example 1.
The prepared nickel cobalt lithium aluminate cathode material of this contrast, the reversible discharge specific capacity under 400mA/g current density
For 160mAh/g, capability retention is 72% after being circulated 200 times using 2C rate charge-discharge.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of hud typed positive electrode of composite cladding, it is characterised in that the hud typed positive electrode includes compound
The kernel that oxide clad anode material is formed, and it is coated on the network combined beyond the region of objective existence shell of three-dimensional manometer of the core surface.
2. hud typed positive electrode according to claim 1, it is characterised in that with total matter of the hud typed positive electrode
Measure and counted for 100%, the gross mass percentage composition of composite oxides and the network combined beyond the region of objective existence shell of three-dimensional manometer in kernel is 0.01
~5%.
3. hud typed positive electrode according to claim 1 or 2, it is characterised in that the average grain diameter of the kernel be 5~
20μm；
Preferably, the positive electrode in kernel is nickel cobalt lithium aluminate；
Preferably, the kernel is formed by the composite oxides cladding nickel cobalt lithium aluminate of cerium, titanium and zirconium, the knot of the kernel
Structure formula is LiNixCoyAlzMO2, 0.45≤x ＜ 1,0≤y≤0.35,0≤z ＜ 0.2；M=CeαTiβZrγ, the ＜ of 0 ＜ α ＜ 0.2,0
The ＜ γ ＜ 0.2 of β ＜ 0.2,0, and 0 ＜ alpha+betas+γ≤0.2；
Preferably, the average thickness of the network combined beyond the region of objective existence shell of the three-dimensional manometer is 0.1~3 μm；
Preferably, the network combined beyond the region of objective existence shell of the three-dimensional manometer is the compound of conducting polymer and conductive carbon material；
Preferably, the conducting polymer is any one in polypyrrole, polyaniline, polythiophene or polyoxyethylene or at least two
Kind mixture, or, the copolymer of any one or at least two above-mentioned polymer monomers；
Preferably, counted using the gross mass of the network combined beyond the region of objective existence shell of the three-dimensional manometer as 100%, the quality of the conducting polymer
Percentage composition is 45~99.99%.
4. hud typed positive electrode according to claim 3, it is characterised in that the network combined beyond the region of objective existence shell of three-dimensional manometer
For the compound of conducting polymer, graphene and CNT；
Preferably, the CNT is any one in single-walled carbon nanotube or multi-walled carbon nanotube or at least two mixing
Thing, preferably multi-walled carbon nanotube；
Preferably, the CNT is the CNT of acidified processing；
Preferably, counted using the gross mass of the network combined beyond the region of objective existence shell of the three-dimensional manometer as 100%, the graphene and CNT
Gross mass percentage composition be 0.01~55%；
Preferably, the mass ratio of the graphene and CNT is m, and 0 ＜ m ＜ 1.
5. the preparation method of the hud typed positive electrode of the composite cladding as described in claim any one of 1-4, its feature
It is, the described method comprises the following steps：
A, first, positive electrode material precursor is mixed with the precursor sol of composite oxides it is scattered, and to obtained dispersion liquid
The middle polyethylene glycol for adding weight/mass percentage composition 0.1~0.5%, mixes with lithium source after spray drying and carries out pyroreaction, obtain
The kernel formed to composite oxides clad anode material；
B, then, the network combined beyond the region of objective existence shell of three-dimensional manometer is coated in the core surface, obtains the hud typed of composite cladding
Positive electrode.
6. according to the method for claim 5, it is characterised in that positive electrode material precursor described in step a is nickel cobalt aluminium forerunner
Body, the preferably hydroxide precursor of the carbonate precursor of nickel cobalt aluminium or nickel cobalt aluminium；
Preferably, the precursor sol of composite oxides described in step a after the hydrolysis of alkoxide of each metal in composite oxides by obtaining
Arrive；
Preferably, the precursor sol of composite oxides described in step a is the mixed sols of cerium, titanium and zirconium, by cerium, titanium and zirconium
Obtained after hydrolysis of alkoxide；
Preferably, lithium source described in step a includes lithium chloride, lithium bromide, lithium phosphate, lithium dihydrogen phosphate, the lithium of phosphoric acid hydrogen two, sulfuric acid
In lithium, lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, lithium benzoate or lithium citrate
Any one or at least two combination, preferably lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium formate,
In lithium citrate or tert-butyl alcohol lithium any one or at least two combination, more preferably lithium carbonate, lithium hydroxide, second
In sour lithium or lithium oxalate any one or at least two combination；
Preferably, pyroreaction described in step a is：Under oxygen atmosphere, 350~650 DEG C of the first temperature is first warming up to,
650~950 DEG C of second temperature insulation is warming up to again；
Preferably, the heating rate for being warming up to first temperature is 1~10 DEG C/min；
Preferably, it is 2~20h in the time of first temperature；
Preferably, the heating rate for being warming up to the second temperature is 1~10 DEG C/min；
Preferably, it is 2~24h in the time of second temperature insulation.
7. the method according to claim 5 or 6, it is characterised in that cladding is in-stiu coating described in step b；
Preferably, the network combined beyond the region of objective existence shell of three-dimensional manometer described in step b is the compound of conducting polymer and conductive carbon material, excellent
Elect the compound of conducting polymer, graphene and CNT as；
Preferably, the CNT is the CNT after acidification, is the step of the acidification：By CNT
It is 3 in volume ratio:Ultrasonic disperse 3h in 1 concentrated sulfuric acid and concentrated nitric acid, 5h then is stirred in 60 DEG C of speed with 800r/min, it is cold
But after, pour into the mixture of ice and water of deionized water, filter, washed to neutrality through cellulose ester membrane, after obtaining acidification
CNT.
8. according to the method for claim 7, it is characterised in that step b is：In the core surface in-stiu coating by polymerizeing
The network combined beyond the region of objective existence shell of three-dimensional manometer that thing, graphene and CNT are formed, specifically includes following steps：
1. adding surfactant into graphene oxide, disperse, then add hydrazine hydrate, product is separated except unnecessary table
Face activating agent, obtain being formed the reduced graphene of micella between graphene layer；
2. the product after step 1. middle separation is scattered in a solvent and ultrasonic, the kernel that step a is obtained then is added thereto,
Continue ultrasonic disperse；
3. adding conducting polymer or monomer into the step 2. product of ultrasonic disperse, continue ultrasound, add ammonium persulfate and
CNT, in ice-water bath stirring carry out polymerisation, product after separation dry, core surface obtain by polymer,
The network combined beyond the region of objective existence shell of three-dimensional manometer that graphene and CNT are formed.
9. according to the method for claim 8, it is characterised in that 1. the surfactant is cetyl trimethyl to step
In ammonium bromide, hexadecyltrimethylammonium chloride, lauryl sodium sulfate or neopelex any one or extremely
Few two kinds mixture；
Preferably, step is 1. described disperses to carry out through ultrasonic wave；
Preferably, 2. the solvent is appointing in the chloroformic solution of ethanol, deionized water, inorganic proton acid or ferric trichloride to step
Anticipate a kind of or at least two mixtures；
Preferably, 2. the time for continuing ultrasonic disperse is 0.5~1h to step；
Preferably, 3. the time for continuing ultrasound is 30~60min to step；
Preferably, the time of the step 3. polymerisation is 18~24h；
Preferably, step 3. the drying temperature be 40~80 DEG C；
Preferably, 3. the drying is 60 DEG C of vacuum drying to step.
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes answering described in claim any one of 1-4
The hud typed positive electrode of condensation material cladding.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244232A (en) * | 2010-05-13 | 2011-11-16 | 天津华夏泓源实业有限公司 | Method for preparing composite lithium cobaltate anode material with high capacity and high compact density |
| CN103647073A (en) * | 2013-12-17 | 2014-03-19 | 惠州亿纬锂能股份有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN104600290A (en) * | 2014-12-30 | 2015-05-06 | 深圳市贝特瑞新能源材料股份有限公司 | Nickel-cobalt lithium aluminate composite positive electrode material and preparation method thereof |
| CN104716320A (en) * | 2015-03-10 | 2015-06-17 | 中国科学院过程工程研究所 | Composite-coated lithium iron phosphate, preparation method of composite-coated lithium iron phosphate, and lithium ion battery |
| CN105304936A (en) * | 2015-12-10 | 2016-02-03 | 微宏动力***（湖州）有限公司 | Lithium ion secondary cell |
-
2017
- 2017-09-27 CN CN201710889122.4A patent/CN107845786B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244232A (en) * | 2010-05-13 | 2011-11-16 | 天津华夏泓源实业有限公司 | Method for preparing composite lithium cobaltate anode material with high capacity and high compact density |
| CN103647073A (en) * | 2013-12-17 | 2014-03-19 | 惠州亿纬锂能股份有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN104600290A (en) * | 2014-12-30 | 2015-05-06 | 深圳市贝特瑞新能源材料股份有限公司 | Nickel-cobalt lithium aluminate composite positive electrode material and preparation method thereof |
| CN104716320A (en) * | 2015-03-10 | 2015-06-17 | 中国科学院过程工程研究所 | Composite-coated lithium iron phosphate, preparation method of composite-coated lithium iron phosphate, and lithium ion battery |
| CN105304936A (en) * | 2015-12-10 | 2016-02-03 | 微宏动力***（湖州）有限公司 | Lithium ion secondary cell |
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