CN105576219B - With three-dimensional Li+Self-healing layered cathode material of diffusion admittance and preparation method thereof - Google Patents
With three-dimensional Li+Self-healing layered cathode material of diffusion admittance and preparation method thereof Download PDFInfo
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Abstract
One kind has three-dimensional Li+The self-healing layered cathode material of diffusion admittance, it is to be used as kernel matrix using layered cathode active material, the high polymer film layer for possessing self-healing capability is uniformly coated with outside it, the nano particle of poly-metal deoxide containing lithium is uniformly inlaid with high polymer film layer to form three-dimensional Li in high polymer film layer+Diffusion admittance structure；Its preparation method comprises the following steps：High polymer material is diluted in organic solvent；Lithium poly-metal deoxide nano particle will be contained to be added in polymer dilution liquid, coating is obtained after stirring；Layered cathode active material is added in coating, is dried after stirring, self-healing layered cathode material is produced after being cooled to room temperature.The structural stability and chemical property of the self-healing layered cathode material of the present invention are significantly improved compared to existing product.
Description
Technical field
The invention belongs to battery material field, more particularly to a kind of self-healing layered cathode material and preparation method thereof.
Background technology
Lithium ion battery has energy density high, operating temperature and operating voltage range is wide, memory-less effect, cycle life
The advantages that long, it is widely used in digital product and electric tool, and is considered as the desired electrical of electric automobile of future generation
Source.In recent years, market proposes higher requirement to lithium ion battery, i.e., higher energy density, high power density, stability and
High security.
Positive electrode is one of critical material for restricting performance of lithium ion battery, and layered cathode material is because having theoretical capacity
Height, cost are low, advantages of environment protection is considered as one of most potential material of lithium ion battery of future generation.By improving just
The performance of pole material, lithium ion battery energy density can be improved, this is mainly reflected in following five aspects：1) increase Ni contents,
Improve capacity；2) high rate performance is improved；3) reinforcing material structural stability, cycle performance of battery is improved；4) compacted density is improved；
5) charge cutoff voltage is improved.Because potential is higher residing for positive electrode, taking off lithium state positive electrode has compared with strong oxidizing property, easily
Side reaction occurs with organic bath, produces gas, causes the deterioration of potential safety hazard and battery performance；Big multiplying power (>10C) fill
Electric discharge, long circulating (>2000 times) and high charge blanking voltage (>Under 4.3V), the side reaction of electrolyte, which is decomposed, to be accelerated, and causes material
Metallic element dissolution, capacity and cycle performance are reduced, especially for Conglobation type second particle, in charge and discharge process, crystal grain
Continuous contraction and expansion, produce new crystal boundary face in material internal, local impedance increase, cause the deterioration of chemical property.
Surface coating is carried out to positive electrode can prevent positive active material from being contacted with the direct of electrolyte, reduce secondary anti-
Answer, the performance of positive electrode can be effectively improved.Conventional cladding material is mostly metal or nonmetallic oxide, metal pentafluoride
Thing, phosphate, carbon material, conducting polymer, high polymer cemented dose etc., they can avoid positive electrode particle directly and electrolyte
Contact.However, in cyclic process, the continuous contraction and expansion of crystal grain, new crystal boundary face is produced in material internal, is answering masterpiece
Under so that be broken originally in the clad of surface of active material, the disappearance of clad effect increases material local impedance
Add, Li+Transport efficiency reduces, and causes the deterioration of chemical property.
As can be seen here, exploitation one kind can give full play to lithium ion battery energy density advantage and disclosure satisfy that charge and discharge repeatedly
The lower crystal grain deformation process performance of electricity does not change, while can also have self-repair function certain non-reversible deformation occurs
Layered cathode material, this will greatly promote the further commercial applications of lithium ion battery, have wide commercial Application
And market promotion prospect.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, there is provided one
What kind structural stability and chemical property were significantly improved has three-dimensional Li+The self-healing layered cathode material of diffusion admittance,
Correspondingly provide it is a kind of it is easy to operate, cost is low, yield is high and is easy to the system of the self-healing layered cathode material of structure regulating
Preparation Method.
In order to solve the above technical problems, technical scheme proposed by the present invention has three-dimensional Li for one kind+Diffusion admittance from
Heal layered cathode material, it is characterised in that the self-healing layered cathode material be using layered cathode active material in
Core matrix, the layered cathode active material are uniformly coated with the high polymer film layer for possessing self-healing capability, the high-polymer membrane outside
The nano particle of poly-metal deoxide containing lithium is uniformly inlaid with layer to form three-dimensional Li in high polymer film layer+Diffusion admittance knot
Structure.
In above-mentioned self-healing layered cathode material, it is preferred that the high polymer material of the high-polymer membrane layer choosing is two
The hydrogen bond selfreparing of the hydrogen bond self-healing polymers, diamido tetraethyl triuret chemical group of acyl aminoethyl urea chemical group gathers
The double phenyl room temperature vulcanized silicone rubbers of compound, methyl, the organic π-π blocked with rich pi-electron pyrenyl stack self-healing polymers, second
One or more in alkene-methacrylic acid copolymer.More preferably the double phenyl room temperature vulcanized silicone rubber of methyl and/or ethene-
Methacrylic acid copolymer.
In above-mentioned self-healing layered cathode material, it is preferred that the nano particle of poly-metal deoxide containing lithium is to be selected from
Spinel-type LiMn2-xAxO4, amblygonite type LiMyZ1-yNO4F, monocline phosphoric acid vanadium lithium type Li1.3Al0.3Ti1.7(PO4)3、
Li3V2(PO4)3At least one of；Wherein, A chooses one kind or more in Ni, Co, Fe, Ti, Mg, Al, Zr, W, Ce, Nb, Y
Kind；0≤x≤0.5；M chooses at least one of Fe, V；N chooses at least one of P, S；Z is chosen in Al, Cr, Y, Ti extremely
Few one kind；0≤y≤1.0.More preferably LiNi0.5Mn1.5O4、Li3V2(PO4)3At least one of.
In above-mentioned self-healing layered cathode material, it is preferred that the particle diameter of the nano particle of poly-metal deoxide containing lithium
It is distributed D50=10nm~200nm；It is furthermore preferred that the particle diameter distribution D of the nano particle of poly-metal deoxide containing lithium50=10nm
~100nm.
In above-mentioned self-healing layered cathode material, it is preferred that layered positive electrode active materials are
LiNixCoyMnzMaO2, wherein, 0≤x≤1,0≤y≤1,0≤z≤1/3；M is chosen in Ti, Mg, Al, Zr, W, Ce, Nb, Y extremely
Few one kind；0≤a≤0.02.
In above-mentioned self-healing layered cathode material, it is preferred that the dosage of high polymer material accounts in the high polymer film layer
The mass fraction of layered cathode active material is no more than 5wt%, the nanometer of poly-metal deoxide containing lithium in the high polymer film layer
The mass fraction that the dosage of grain accounts for layered cathode active material is no more than 3wt%, and the nano particle of poly-metal deoxide containing lithium
Quality is less than the quality of high polymer material.
The technical concept total as one, the present invention also provide a kind of preparation side of above-mentioned self-healing layered cathode material
Method, comprise the following steps：
(1) preparation of high polymer dilution：Above-mentioned high polymer material is diluted in organic solvent to obtain high polymer dilute
Release liquid；
(2) preparation of coating：The above-mentioned nano particle of poly-metal deoxide containing lithium is added into above-mentioned steps (1) to be made
Polymer dilution liquid in, be dispersed with stirring uniformly after, obtain coating；
(3) coat：Described layered cathode active material is added in coating made from above-mentioned steps (2), stirred
After being uniformly dispersed, first forced air drying, then be dried in vacuo, produce self-healing layered cathode material after being cooled to room temperature.
The preparation method of above-mentioned self-healing layered cathode material, it is preferred that high polymer material in the high polymer dilution
The control of the volume ratio of material and organic solvent is 1: 1~100.
The preparation method of above-mentioned self-healing layered cathode material, it is preferred that the organic solvent is chloroform, N-N diformazans
One kind in base pyrrolidones, N,N-dimethylformamide.
The technical scheme of the invention described above is based primarily upon following principle and thinking：By the way that high polymer material and three will can be formed
Tie up Li+The nano material of poly-metal deoxide containing the lithium stirring of diffusion admittance type structure is mixed, and forms layered cathode material surface
One layer has three-dimensional Li+The uniform selfreparing high polymer film layer of diffusion admittance, it is steady can to effectively improve layered cathode material surface
Qualitative and chemical property；Wherein, high-polymer membrane provides mechanical strength and self-repair function, after deforming upon, although material
Surface can be crosslinked reaction again by related functional group in strand and be reviewed one's lessons by oneself so as to realize there occurs molecular chain rupture
Multiple function, and then improve the structural stability and cycle performance of material；Further, we are uniform also in high polymer film layer
The nano material of poly-metal deoxide containing lithium is inlayed, i.e., we are dexterously load by the high polymer film layer with self-repair function
Body, also three-dimensional is being constructed between layered cathode active material core matrix and electrolyte on the basis of realizing self-repair function
Li+Diffusion admittance, this just further increases the high rate performance of positive electrode.
Compared with prior art, the advantage of the invention is that：
1) clad of layered cathode active material core matrix of the invention is by the high polymer material with self-healing capability
Material is with having three-dimensional Li+The nano material of poly-metal deoxide containing the lithium mixing composition of diffusion admittance structure, layered cathode activity
The structural stability and chemical property of material are significantly improved relative to common positive electrode.
2) the high polymer film layer in layered cathode material of the invention provides mechanical strength and self-repair function, and shape is occurring
After change, although material surface there occurs molecular chain rupture, but still can be crosslinked instead again by related functional group in strand
The structural stability and cycle performance of material should be further improved so as to realize the function of selfreparing；
3) in layered cathode material clad of the invention, the nano material of poly-metal deoxide containing lithium forms three-dimensional Li+
Diffusion admittance structure, three-dimensional Li can be provided between layered cathode active material core matrix and electrolyte+Diffusion admittance, improve
The ionic conductivity of clad, accelerate Li+Diffusion rate, improve high rate performance.
4) preparation method of the invention is added directly into polymer dilution by that will contain lithium poly-metal deoxide nano particle
Mixed in liquid, directly coated and dried (rather than calcining) after mixing, this has not only broken existing conventional operation
Technique, and have the characteristics that easy to operate, cost is low, yield is high and be easy to structure regulating.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
These accompanying drawings obtain other accompanying drawings.
Fig. 1 is the SEM figures of pole piece after the embodiment of the present invention 2 circulates 51 weeks.
Fig. 2 is the SEM figures of pole piece after comparative example 1 of the present invention circulates 51 weeks.
Fig. 3 is the embodiment of the present invention 2 and comparative example 1,2 curve of double curvature figures.
Fig. 4 is the embodiment of the present invention 2 and comparative example 1,2 cyclic curve figures.
Fig. 5 is the structural representation of self-healing layered cathode material of the present invention.
Fig. 6 is the structural representation of positive electrode shown in comparative example 1 in embodiment.
Fig. 7 has three-dimensional Li for the present invention+The section structure diagram of the self-healing layered cathode material of diffusion admittance.
Embodiment
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of present invention's as shown in Figure 5, Figure 7 has three-dimensional Li+The self-healing layered cathode material of diffusion admittance, should be certainly
The layered cathode material that heals is with layered cathode active material LiCo0.995Ti0.002Mg0.003O2As kernel matrix, the stratiform is just
The high polymer film layer for possessing self-healing capability is uniformly coated with outside the active material of pole, is uniformly inlaid with high polymer film layer more containing lithium
Metal oxide nanoparticles in high polymer film layer to form three-dimensional Li+Diffusion admittance structure.The height of high-polymer membrane layer choosing
Polymer material is the double phenyl room temperature vulcanized silicone rubbers of methyl.The nano-particle material of poly-metal deoxide containing lithium is to be selected from amblygonite
Type LiFePO4F, the particle diameter distribution D of the nano particle of poly-metal deoxide containing lithium50=20nm.High polymer material in high polymer film layer
Dosage to account for the mass fraction of layered cathode active material be 3wt%, the nanometer of poly-metal deoxide containing lithium in high polymer film layer
The mass fraction that the dosage of grain accounts for layered cathode active material is 2wt%, and the quality of the nano particle of poly-metal deoxide containing lithium
Less than the quality of high polymer material.
A kind of preparation method of above-mentioned self-healing layered cathode material, comprises the following steps：
(1) preparation of high polymer dilution：By the double phenyl room temperature vulcanized silicone rubbers of 3g methyl according to 1: 50 volume ratio
It is diluted in chloroform and obtains high polymer dilution；
(2) preparation of coating：By 2g nanometers LiFePO4F is added in the high polymer dilution of above-mentioned steps (1), is stirred
Mix after being uniformly dispersed, obtain coating；
(3) coat：By 100g layered cathode active materials LiCo0.995Ti0.002Mg0.003O2It is added to above-mentioned steps (2) system
In the coating obtained, after being dispersed with stirring uniformly, 24h is first dried in 40 DEG C of air dry ovens, then in 100 DEG C of vacuum drying chambers
Room temperature is cooled to after vacuum drying 10h, is produced with three-dimensional Li+The self-healing layered cathode material of diffusion admittance.
There is three-dimensional Li by manufactured in the present embodiment+The self-healing layered cathode material of diffusion admittance makes CR2032 types and buckled
Formula battery, determines its chemical property, and concrete numerical value see the table below 1.Test voltage is 3.0-4.5V, and battery is carried out at normal temperatures
Multiplying power and loop test：3.0C/0.2C=93.0%；Under 1C/1C charge and discharge cycles, 51 weeks capability retentions are 94.8%, table
Preferable multiplying power and cycle performance are revealed.
Table 1：The electrochemical property test contrast table of each embodiment and comparative example
Embodiment 2：
A kind of present invention's as shown in Figure 5, Figure 7 has three-dimensional Li+The self-healing layered cathode material of diffusion admittance, should be certainly
The layered cathode material that heals is with layered cathode active material LiNi0.6Co0.2Mn0.197Al0.003O2As kernel matrix, the stratiform
The high polymer film layer for possessing self-healing capability is uniformly coated with outside positive electrode active materials, is uniformly inlaid with containing lithium in high polymer film layer
Poly-metal deoxide nano particle in high polymer film layer to form three-dimensional Li+Diffusion admittance structure.High-polymer membrane layer choosing
High polymer material is ethylene-methacrylic acid copolymer.The nano-particle material of poly-metal deoxide containing lithium is to be selected from spinel-type
LiNi0.5Mn1.5O4, the particle diameter distribution D of the nano particle of poly-metal deoxide containing lithium50=50nm.High polymer material in high polymer film layer
The mass fraction that the dosage of material accounts for layered cathode active material is 4wt%, the nanometer of poly-metal deoxide containing lithium in high polymer film layer
The mass fraction that the dosage of particle accounts for layered cathode active material is 2.5wt%, and the nano particle of poly-metal deoxide containing lithium
Quality is less than the quality of high polymer material.
A kind of preparation method of above-mentioned self-healing layered cathode material, comprises the following steps：
(1) preparation of high polymer dilution：4g ethylene-methacrylic acid copolymers is dilute according to 1: 100 volume ratio
Release and high polymer dilution is obtained in N-N dimethyl pyrrolidones；
(2) preparation of coating：By 2.5g spinel type nanometers LiNi0.5Mn1.5O4The height for being added to above-mentioned steps (1) gathers
In thing dilution, after being dispersed with stirring uniformly, coating is obtained；
(3) coat：By 100g layered cathode active materials LiNi0.6Co0.2Mn0.197Al0.003O2It is added to above-mentioned steps (2)
In obtained coating, after being dispersed with stirring uniformly, 24h is first dried in 40 DEG C of air dry ovens, then in 100 DEG C of vacuum drying chambers
Room temperature is cooled to after middle vacuum drying 10h, is produced with three-dimensional Li+The self-healing layered cathode material of diffusion admittance.
Comparative example 1：
One kind has three-dimensional Li as shown in Figure 6+The layered cathode material of diffusion admittance, layered cathode active matrix are
LiNi0.6Co0.2Mn0.197Al0.003O2, three-dimensional Li+The nano material of diffusion admittance structure is spinel-type LiNi0.5Mn1.5O4.Bag
Nanometer LiNi in coating0.5Mn1.5O4Account for the mass fraction 2.5wt% of layered cathode active matrix, nanometer LiNi0.5Mn1.5O4's
D50For 50nm.
There is three-dimensional Li above+The preparation method of the layered cathode material of diffusion admittance, comprises the following steps：
1) by 100g layered cathode active matrix LiNi0.6Co0.2Mn0.197Al0.003O2With 2.5g nanometers LiNi0.5Mn1.5O4
It is placed in ball milling in ball grinder, ratio of grinding media to material 1: 1, Ball-milling Time 3.5h, rotating speed 1000rpm；Batch mixing obtains compound after terminating；
2) coat：Obtained compound is placed in 550 DEG C of clock hood type furnaces and sinters 8h, after Temperature fall, crosses 300 mesh Buddhist nuns by hand
Imperial screen cloth, produce comparative example 1 has three-dimensional Li+The layered cathode material of diffusion admittance.
Comparative example 2：
A kind of self-healing layered cathode material, layered cathode active matrix materials are LiNi0.6Co0.2Mn0.197Al0.003O2,
High polymer is ethylene-methacrylic acid copolymer.Ethylene-methacrylic acid copolymer accounts for layered cathode active matrix in clad
The mass fraction of material is 4wt%.
The preparation method of above self-healing layered cathode material, comprises the following steps：
1) preparation of high polymer dilution：4g ethylene-methacrylic acid copolymers are diluted according to 1: 100 volume ratio
High polymer dilution is obtained in N-N dimethyl pyrrolidones；
2) coat：By 100g layered cathode active matrix LiNi0.6Co0.2Mn0.197Al0.003O2Matrix is added to step 1)
In high polymer dilution, after being dispersed with stirring uniformly, 24h is first dried in 40 DEG C of air dry ovens, then in 100 DEG C of vacuum drying chambers
Room temperature is cooled to after vacuum drying 10h, produces the healing layered cathode material of comparative example 2.
Three kinds of positive electrodes made from above-described embodiment 2 and comparative example 1,2 are fabricated to CR2032 type button cells.Often
Its chemical property is determined under temperature, specifically sees the above table 1 and Fig. 3, Fig. 4, test voltage 2.8-4.25V；The multiplying power of embodiment 2
3.0C/0.2C is 89.2%；After 51 weeks loop tests, the capability retention of battery is 97.6%.With 1 bag of comparative example
It is spinel-type LiNi to cover nano material0.5Mn1.5O4Compare, the multiplying power 3.0C/0.2C of comparative example 1 is 90.0%；But by 51
After all loop tests, the capability retention of battery is only 88.6%, it is seen that lithium ion cell positive prepared by the embodiment of the present invention 2
The cycle performance of material is improved significantly.Compared with 2 cladding ethylene-methacrylic acid copolymers of comparative example, comparative example 2
Multiplying power 3.0C/0.2C is 86.4%；After 51 weeks loop tests, the capability retention of battery is 96.7%, it is seen that the present invention
The high rate performance of anode material for lithium-ion batteries prepared by embodiment 2 significantly improves.
The pole piece of button cell takes out after above-described embodiment 2 and comparative example 1 are circulated, and carries out SEM tests.As shown in Figure 1, Figure 2
Shown, comparative example 1 is after continuous discharge and recharge, and a crystal grain constantly shrinks and expansion so that particle has obvious rupture, and wraps
The embodiment 2 of self-healing high polymer is covered, the pattern of material is substantially without too big change.
Embodiment 3：
A kind of present invention's as shown in Figure 5, Figure 7 has three-dimensional Li+The self-healing layered cathode material of diffusion admittance, should be certainly
The layered cathode material that heals is with layered cathode active material LiNi0.8Co0.1Mn0.1O2As kernel matrix, the layered cathode is lived
Property material outside be uniformly coated with the high polymer film layer for possessing self-healing capability, be uniformly inlaid with high polymer film layer containing the more metals of lithium
Oxide nano particles in high polymer film layer to form three-dimensional Li+Diffusion admittance structure.The high polymer of high-polymer membrane layer choosing
Material is ethylene-methacrylic acid copolymer+methyl double phenyl room temperature vulcanized silicone rubbers (concretely double phenyl room temperatures of dimethyl
Sulphurated siliastic) (mass ratio 1: 1).The nano-particle material of poly-metal deoxide containing lithium is to be selected from phosphoric acid vanadium lithium type Li3V2
(PO4)3, the particle diameter distribution D of the nano particle of poly-metal deoxide containing lithium50=100nm.The use of high polymer material in high polymer film layer
The mass fraction that amount accounts for layered cathode active material is 4wt%, the nano particle of poly-metal deoxide containing lithium in high polymer film layer
The mass fraction that dosage accounts for layered cathode active material is 2.5wt%, and the quality of the nano particle of poly-metal deoxide containing lithium is small
In the quality of high polymer material.
A kind of preparation method of above-mentioned self-healing layered cathode material, comprises the following steps：
(1) preparation of high polymer dilution：By 2.0g ethylene-methacrylic acid copolymers and the double phenyl room temperatures of 2.0g methyl
Sulphurated siliastic is diluted in N-N dimethylformamides according to 1: 50 volume ratio and obtains high polymer dilution；
(2) preparation of coating：By 2.5g nanometers Li3V2(PO4)3It is added to the high polymer dilution of above-mentioned steps (1)
In, after being dispersed with stirring uniformly, obtain coating；
(3) coat：By 100g layered cathode active materials LiNi0.8Co0.1Mn0.1O2It is obtained to be added to above-mentioned steps (2)
In coating, after being dispersed with stirring uniformly, 24h, then the vacuum in 100 DEG C of vacuum drying chambers are first dried in 40 DEG C of air dry ovens
Room temperature is cooled to after drying 10h, is produced with three-dimensional Li+The self-healing layered cathode material of diffusion admittance.
There is three-dimensional Li by manufactured in the present embodiment+The self-healing layered cathode material of diffusion admittance is fabricated to CR2032 types
Button cell, determines its chemical property, and concrete numerical value is shown in Table 1.Test voltage is 3.0-4.3V, and battery is carried out at normal temperatures
Multiplying power and loop test：3.0C/0.2C=89.8%；Under 1C/1C charge and discharge cycles, 51 weeks capability retentions are 97.0%, table
Preferably multiplying power and cycle performance are revealed.
Claims (9)
1. one kind has three-dimensional Li+The self-healing layered cathode material of diffusion admittance, it is characterised in that the self-healing stratiform is just
Pole material is using layered cathode active material as kernel matrix, is uniformly coated with outside the layered cathode active material and possesses self-healing
The high polymer film layer of conjunction ability, the nano particle of poly-metal deoxide containing lithium is uniformly inlaid with the high polymer film layer with poly- in height
Three-dimensional Li is formed in thing film layer+Diffusion admittance structure.
2. self-healing layered cathode material according to claim 1, it is characterised in that the height of the high-polymer membrane layer choosing
Polymer material is the hydrogen bond self-healing polymers of diamide ethyl carbamide chemical group, diamido tetraethyl triuret chemical group
The double phenyl room temperature vulcanized silicone rubbers of hydrogen bond self-healing polymers, methyl, stacked and reviewed one's lessons by oneself with organic π-π of rich pi-electron pyrenyl end-blocking
One or more in multiple polymer, ethylene-methacrylic acid copolymer.
3. self-healing layered cathode material according to claim 1, it is characterised in that the poly-metal deoxide containing lithium
Nano particle is to be selected from spinel-type LiMn2-xAxO4, amblygonite type LiMyZ1-yNO4F, monocline phosphoric acid vanadium lithium type
Li1.3Al0.3Ti1.7(PO4)3、Li3V2(PO4)3At least one of；
Wherein, A chooses the one or more in Ni, Co, Fe, Ti, Mg, Al, Zr, W, Ce, Nb, Y；0≤x≤0.5；M selections Fe,
At least one of V；N chooses at least one of P, S；Z chooses at least one of Al, Cr, Y, Ti；0≤y≤1.0.
4. self-healing layered cathode material according to claim 3, it is characterised in that the poly-metal deoxide containing lithium is received
The particle diameter distribution D of rice grain50=10nm~200nm.
5. self-healing layered cathode material according to claim 1, it is characterised in that layered positive electrode active materials are
LiNixCoyMnzMaO2, wherein, 0≤x≤1,0≤y≤1,0≤z≤1/3；M is chosen in Ti, Mg, Al, Zr, W, Ce, Nb, Y extremely
Few one kind；0≤a≤0.02；It is 0 when x, y, z and a differences.
6. the self-healing layered cathode material according to any one of claim 1-5, it is characterised in that the high polymer
The dosage of high polymer material accounts for the mass fraction of layered cathode active material and is no more than 5 wt%, the high polymer film layer in film layer
In the dosage of the nano particle of poly-metal deoxide containing lithium account for the mass fraction of layered cathode active material and be no more than 3 wt%, and contain
The quality of lithium poly-metal deoxide nano particle is less than the quality of high polymer material.
7. a kind of preparation method of self-healing layered cathode material as any one of claim 1-6, including following step
Suddenly：
（1）The preparation of high polymer dilution：High polymer material is diluted in organic solvent and obtains high polymer dilution；
（2）The preparation of coating：Lithium poly-metal deoxide nano particle will be contained and be added to above-mentioned steps（1）Obtained polymer is dilute
Release in liquid, after being dispersed with stirring uniformly, obtain coating；
（3）Cladding：Described layered cathode active material is added to above-mentioned steps（2）In obtained coating, it is dispersed with stirring
After uniformly, first forced air drying, then be dried in vacuo, produce self-healing layered cathode material after being cooled to room temperature.
8. the preparation method of self-healing layered cathode material according to claim 7, it is characterised in that the high polymer is dilute
It is 1: 1~100 to release the volume ratio of high polymer material and organic solvent control in liquid.
9. the preparation method of the self-healing layered cathode material according to claim 7 or 8, it is characterised in that described organic
Solvent is one kind in chloroform, N-N dimethyl pyrrolidones, N,N-dimethylformamide.
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| CN104919626A (en) * | 2012-11-09 | 2015-09-16 | 里兰斯坦福初级大学理事会 | Seal-healing composites and applications thereof |
| CN105098143A (en) * | 2014-05-16 | 2015-11-25 | 中国科学院金属研究所 | Flexible high-sulfur load self-repairing cathode structure for lithium-sulfur battery and preparation method of flexible high-sulfur load self-repairing cathode structure |
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| CN104919626A (en) * | 2012-11-09 | 2015-09-16 | 里兰斯坦福初级大学理事会 | Seal-healing composites and applications thereof |
| CN105098143A (en) * | 2014-05-16 | 2015-11-25 | 中国科学院金属研究所 | Flexible high-sulfur load self-repairing cathode structure for lithium-sulfur battery and preparation method of flexible high-sulfur load self-repairing cathode structure |
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