CN108807933A - A kind of positive electrode and preparation method thereof - Google Patents
A kind of positive electrode and preparation method thereof Download PDFInfo
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- CN108807933A CN108807933A CN201810704189.0A CN201810704189A CN108807933A CN 108807933 A CN108807933 A CN 108807933A CN 201810704189 A CN201810704189 A CN 201810704189A CN 108807933 A CN108807933 A CN 108807933A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention provides a kind of positive electrodes, including ternary material and the clad for being coated on the ternary material surface, and the material of the clad includes organic fire proofing.Positive electrode provided by the invention does not have a negative impact to electrical property, greatly improves the thermal stability of tertiary cathode material and the chemical property of battery by coating organic fire proofing on ternary material surface while inhibiting electrolyte to burn.The present invention also provides a kind of preparation methods of positive electrode, including：Ternary material is taken, ternary material is sufficiently mixed in a solvent with covering material, obtains mixed solution, covering material includes organic fire proofing；Mechanical fusion is carried out after mixed solution is spray-dried, and obtains the ternary material of clad cladding, i.e. positive electrode.The binding force between clad and ternary material can be further improved by using mechanofusion method.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of positive electrode and preparation method thereof.
Background technology
With the rapid growth of new-energy automobile industry, high energy density cells are increasingly favored in market.Tertiary cathode
Material has received constantly pursuing for market by high gram volume and preferable cyclical stability.But existing tertiary cathode material
Thermostabilization is poor, at a temperature of 200 DEG C or so, will decompose and release oxygen, oxygen and the flammable electrolysis in battery
The heat that liquid, carbon material, bonding agent etc. generate together can be further exacerbated by the decomposition of anode, " thermal runaway " be caused, extremely short
In time will detonation, there are larger security risks.
Clad usually is formed to improve thermal stability on tertiary cathode material surface at present, and someone is in tertiary cathode material
Surface coat various materials in the hope of improving thermal stability, but up to the present, the thermostabilization of positive electrode is promoted
It is limited, the still not up to requirement of industry.
Invention content
In consideration of it, the present invention provides a kind of positive electrode and preparation method thereof, by being coated on ternary material surface
Machine fire proofing will not reduce the internal resistance of battery while inhibiting electrolyte to burn, and not generate negative shadow to electrical property
It rings, greatly improves the thermal stability of tertiary cathode material and the chemical property of battery.
First aspect present invention provides a kind of positive electrode, including ternary material and is coated on the ternary material surface
Clad, the material of the clad includes organic fire proofing.
The positive electrode that first aspect present invention provides is being pressed down by coating organic fire proofing on ternary material surface
While having made electrolyte burning, does not have a negative impact to electrical property, greatly improve the thermostabilization of tertiary cathode material
The chemical property of property and battery.
Wherein, the material of the clad further includes at least one of nano inorganic material and electrochemical active material.
Wherein, mass fraction of the clad in the positive electrode is a, wherein 0<A≤20%.
Wherein, the organic fire-resisting material is cyclotrinitrile phosphide, and the cyclotrinitrile phosphide includes hexa methoxy
Three phosphonitrile of ring, hexaphenoxycyclotriphosphazene, three phosphonitrile of pregnancy basic ring, six pairs of aldehyde radical phenoxy cyclotriphosphazenes and ethyoxyl (five fluorine)
It is one or more in three phosphonitrile of ring.
Wherein, the nano inorganic material includes aluminium oxide, zirconium oxide, cerium oxide, titanium oxide, barium titanate, silica
With it is one or more in conductive carbon black, and/or, the electrochemical active material includes LiFePO4, lithium ferric manganese phosphate, phosphoric acid
Vanadium lithium, vanadium phosphate oxygen lithium and fluorophosphate vanadium lithium are one or more.
Wherein, the pH of the positive electrode is 10.0-11.5.
Wherein, the material of the clad includes finely dispersed organic fire-resisting material, nano inorganic material and electrochemistry
Active material, the organic fire-resisting material, the nano inorganic material and the electrochemical active material are in the positive electrode
In mass fraction be respectively b, c and d, wherein 0<B≤2%, 0<C≤16%, 0<D≤2%.
Second aspect of the present invention provides a kind of preparation method of positive electrode, includes the following steps：
Ternary material is taken, the ternary material is sufficiently mixed in a solvent with covering material, obtains mixed solution, it is described
Covering material includes organic fire proofing；
Mechanical fusion is carried out after the mixed solution is spray-dried, and obtains the ternary material of clad cladding, i.e.,
Positive electrode, the covering material include organic fire proofing.
The preparation method for the positive electrode that second aspect of the present invention provides obtains covering material first by spray drying
The ternary material powder of cladding.In addition, so that covering material and the binding force of ternary material is improved by mechanofusion method again, to
So that covering material is coated even closer, improve the bulk density of finally obtained positive electrode, and also improves anode
The specific capacity of material improves the electrochemical stability of positive electrode.And preparation method provided by the invention is simple for process, at
This is cheap, is suitable for large-scale production, has very strong practicability.
Wherein, the covering material further includes at least one of nano inorganic material and electrochemical active material, described
Preparation method specifically includes following steps：
Take ternary material, by least one of nano inorganic material and electrochemical active material and the ternary material with
And the organic fire-resisting material is sufficiently mixed in a solvent, obtains mixed solution, after the mixed solution is spray-dried
Mechanical fusion is carried out, positive electrode is obtained.
Wherein, the temperature of the spray drying is 80-250 DEG C, and/or, the rotating speed of the mechanical fusion is 3000-
The time of 5500rpm, the mechanical fusion are 3-20min.
Description of the drawings
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to required in the embodiment of the present invention
The attached drawing used illustrates.
Fig. 1 is the scanning electron microscope (SEM) photograph of positive electrode in the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of raw material NCM523 in the embodiment of the present invention 1；
Fig. 3 be the embodiment of the present invention 1 in it is spray-dried after material scanning electron microscope (SEM) photograph；
Fig. 4 be the embodiment of the present invention 1 in it is spray-dried after material and positive electrode charge-discharge test curve graph；
Fig. 5 be the embodiment of the present invention 2 in it is spray-dried after material scanning electron microscope (SEM) photograph；
Fig. 6 is the scanning electron microscope (SEM) photograph of positive electrode in the embodiment of the present invention 2.
Specific implementation mode
It is the preferred embodiment of the present invention below, it is noted that for those skilled in the art,
Various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as this hair
Bright protection domain.
A kind of positive electrode provided in an embodiment of the present invention, including ternary material and it is coated on the ternary material surface
The material of clad, the clad includes organic fire proofing.
Organic fire-resisting material can form layer protective layer on ternary material surface, it is suppressed that the oxidation process of ternary material.
And under non-normal use state, when short circuit occurs for inside lithium ion cell, moment generates high temperature.At this time organic fire-resisting material by
Heat absorbs heat and simultaneously gasifies, and to reduce the temperature of combustible, and dilutes the dense of gasification of combustible material object and combustion-supporting property gas
Degree reduces the heat transfer between oxygen diffusion, gas phase and solid phase, it is suppressed that the vigorous reaction under battery thermal runaway state, resistance
Only burning sprawling prevents the generation of the precarious positions such as explosion.And for organic fire-resisting material compares inorganic anti-flaming material, to electricity
Performance does not have a negative impact.
It can be seen from the above content that positive electrode provided in an embodiment of the present invention, by being coated on ternary material surface
Machine fire proofing does not have a negative impact to electrical property, is greatly improving ternary just while inhibiting electrolyte to burn
The thermal stability of pole material and the chemical property of battery.In embodiment of the present invention, the material of the clad further includes receiving
Rice at least one of inorganic material and electrochemical active material.Specifically, the material of clad can also be nano inorganic
Material, electrochemical active material or nano inorganic material and electrochemical active material.Nano inorganic material is in addition to that can improve just
Except the thermostabilization of pole material, the residual lithium amount on surface layer can also be reduced, promotes cycle performance.And electrochemical active material is in addition to can
Except the thermostabilization of positive electrode, it is also prevented from the moisture that ternary material absorbs in environment and goes bad, improve positive electrode
Stability and cycle performance.Preferably, the material of clad includes organic fire proofing, nano inorganic material and electro-chemical activity
Material.Their mutual supplement with each other's advantages can be greatlyd improve into thermal stability, the cycle of positive electrode by the synergistic effect of three
Performance, specific capacity, the performances such as multiplying power.
In embodiment of the present invention, mass fraction of the clad in the positive electrode is a, wherein 0<a≤
20%.The content of clad should not be too many, if the content of clad is excessive, the thickness of clad can be caused blocked up, instead can
Hinder positive electrode in the transport of charge and discharge process intermediate ion or electronics.And we can also from the mass fraction of clad
It is e to go out mass fraction of the ternary material in positive electrode, wherein 80%≤e<100%.Preferably, 3≤a≤17%.It is more excellent
Selection of land, 8≤a≤14%.
In embodiment of the present invention, the thickness of the clad can be configured according to actual needs, such as the thickness of clad
Degree can be nanoscale, specific such as 50-2000nm.
In embodiment of the present invention, the organic fire-resisting material is cyclotrinitrile phosphide, the cyclotrinitrile phosphide
Including three phosphonitrile of hexakis-methoxy basic ring, hexaphenoxycyclotriphosphazene, three phosphonitrile of pregnancy basic ring, six pairs of aldehyde radical phenoxy cyclotriphosphazenes and
It is one or more in three phosphonitrile of ethyoxyl (five fluorine) ring.
Cyclotrinitrile phosphide is one kind of organic fire-resisting material, is also one kind best suitable for positive electrode.Ring
The fire retardant mechanism of three phosphazene compounds shows as the comprehensive function of four kinds of approach, and first, heat absorption is cooler when phosphonitrile thermally decomposes
Reason；Its phosphoric acid thermally decomposed to generate, metaphosphoric acid and polyphosphoric acid can form one layer of fixedness on the surface of polymer material and protect
Cuticula has completely cut off air, this is isolation film mechanism；Second, while releasing carbon dioxide, ammonia, nitrogen, water vapour etc. after being heated
Gas, this is diluents mechanism；Third, these non-inflammable gas have blocked the supply of oxygen, realize fire-resistant synergistic and collaboration
Purpose, the 4th, when polymer combustion, has PO groups to be formed, it can be combined with H, HO active group in flame region, play suppression
The effect of flame processed, this is to terminate chain mechanism.Due to acting synergistically above, system shows good flame retardant property, into
Improve to one step the thermal stability of tertiary cathode material.
In embodiment of the present invention, the nano inorganic material includes aluminium oxide, zirconium oxide, cerium oxide, titanium oxide, metatitanic acid
It is one or more in barium, silica and conductive carbon black.Optionally, the conductive carbon black includes C45 etc..
In embodiment of the present invention, the electrochemical active material include LiFePO4, lithium ferric manganese phosphate, phosphoric acid vanadium lithium,
Vanadium phosphate oxygen lithium and fluorophosphate vanadium lithium are one or more.
In embodiment of the present invention, the positive electrode includes cobalt nickel lithium manganate ternary material or nickel cobalt lithium aluminate ternary material
Material；The molecular formula of the cobalt nickel lithium manganate ternary material is LiNi(1-x1-y1)Cox1Mny1O2, wherein 0.1≤x1≤0.4、0.1≤
y1≤ 0.4, the molecular formula of the nickel cobalt lithium aluminate ternary material is LiNi(1-x2-y2)Cox2Aly2O2, wherein 0.1≤x2≤
0.15、0.05≤y2≤0.1。
In embodiment of the present invention, the grain size of the nano inorganic material is 8-60nm, and/or, the electro-chemical activity
The grain size of material is 30-200nm.Preferably, the grain size of the nano inorganic material is 15-40nm, and/or, the electrochemistry
The grain size of active material is 50-170nm.It is highly preferred that the grain size of the nano inorganic material is 20-30nm, and/or, it is described
The grain size of electrochemical active material is 80-130nm.
In embodiment of the present invention, the carbon content of the electrochemical active material is 0.5%-2%.Electrochemical active material
In carbon influence whether the specific capacity of positive electrode.Therefore the carbon content of 0.5%-2% can greatly improve positive electrode
Specific capacity.Preferably, the carbon content of the electrochemical active material is 0.8%-1.6%.It is highly preferred that the electrochemistry is lived
Property material carbon content be 1.1%-1.3%.
In embodiment of the present invention, the pH of the positive electrode is 10.0-11.5.The present invention passes through on ternary material surface
Organic fire proofing or organic fire-resisting material and at least one of nano inorganic material and electrochemical active material are coated, it can pole
The earth reduces the pH of positive electrode, is conducive to the processing of later stage positive electrode so that be not easy to form fruit in the mixing process in later stage
Freeze shape.Optionally, the pH of the positive electrode is 10.2-10.8.When the material of clad further includes electrochemical active material,
Electrochemical active material can further reduce the pH value of positive electrode.Still optionally further, the pH of the positive electrode is
10.4-10.6。
In embodiment of the present invention, the material of the clad includes finely dispersed organic fire-resisting material, nano inorganic
Material and electrochemical active material, the organic fire-resisting material, the nano inorganic material and the electrochemical active material exist
Mass fraction in the positive electrode is respectively b, c and d, wherein 0<B≤2%, 0<C≤16%, 0<D≤2%.The present invention
One embodiment is that three kinds of organic fire-resisting material, nano inorganic material and electrochemical active material materials exist and are coated on
The surface of ternary material, by the synergistic effect of three, by their mutual supplement with each other's advantages, the heat that can greatly improve positive electrode is steady
Qualitative, cycle performance, specific capacity, the performances such as multiplying power.
A kind of preparation method of positive electrode provided in an embodiment of the present invention, includes the following steps：
Step 1：Ternary material is taken, the ternary material is sufficiently mixed in a solvent with covering material, obtains mixing molten
Liquid；The covering material includes organic fire proofing；
Step 2：Mechanical fusion is carried out after the mixed solution is spray-dried, and obtains the ternary material of clad cladding
Material, i.e. positive electrode.
The preparation method of positive electrode provided in an embodiment of the present invention obtains covering material packet first by spray drying
The ternary material powder covered.In addition, making covering material and the binding force of ternary material improve by mechanofusion method again, to make
Covering material coats even closer, improves the bulk density of finally obtained positive electrode, and also improves positive material
The specific capacity of material improves the electrochemical stability of positive electrode.And preparation method provided by the invention is simple for process, cost
It is cheap, it is suitable for large-scale production, there is very strong practicability.
In embodiment of the present invention, the solvent includes liquid dispersant.The liquid dispersant includes N- methylpyrroles
It is one or more in alkanone (NMP), second alcohol and water.
In embodiment of the present invention, the temperature of the spray drying is 80-250 DEG C, and/or, when spray drying, sprays
The pressure of mouth is 0.1-0.5MPa.
In embodiment of the present invention, the rotating speed of mechanical fusion is 3000-5500rpm, and the time of mechanical fusion is 3-
20min。
In embodiment of the present invention, the material of the clad further includes in nano inorganic material and electrochemical active material
At least one, the preparation method specifically includes following steps：
Take ternary material, by least one of nano inorganic material and electrochemical active material and the ternary material with
And organic fire-resisting material is sufficiently mixed in a solvent, obtains mixed solution, is carried out after the mixed solution is spray-dried
Mechanical fusion obtains positive electrode.
The embodiment of the present invention is additionally provided when the material of clad is in nano inorganic material and electrochemical active material
At least one preparation method with when organic fire-resisting material, simple process and low cost is honest and clean, is suitable for large-scale production, has very
Strong practicability.
Multiple embodiments are classified into below to be described further embodiments of the present invention.
Embodiment 1
A kind of preparation method of positive electrode, includes the following steps：
Step 1：NCM523, aluminium oxide, LiFePO4 and hexaphenoxycyclotriphosphazene are taken, according to mass ratio NCM523:Oxygen
Change aluminium:LiFePO4:Hexaphenoxycyclotriphosphazene=95:1:3:1 ratio, which is added in ethanol solution, to be uniformly dispersed, fully mixed
It closes, obtains mixed solution.Then the mixed solution is dried under spray drying device with 150 DEG C of temperature, at this time
The pressure for being spray-dried machine nozzle is 0.2MPa, obtains aluminium oxide, LiFePO4 and hexaphenoxycyclotriphosphazene three cladding
NCM523。
Step 2：Weigh aluminium oxide made from 350g steps 1, LiFePO4 and hexaphenoxycyclotriphosphazene three cladding
NCM523 obtains positive electrode, with NCM523@A tables to merge processing 5min under the rotating speed of 5000rpm in mechanical fusion machine
Show.
Embodiment 2
A kind of preparation method of positive electrode, includes the following steps：
Step 1：Three phosphonitrile of NCM622, C45, lithium ferric manganese phosphate and ethyoxyl (five fluorine) ring is taken, according to mass ratio NCM622:
C45:Lithium ferric manganese phosphate:Three phosphonitrile=93 of ethyoxyl (five fluorine) ring:1:5:1 ratio, which is added in ethanol solution, to be uniformly dispersed,
It is sufficiently mixed, obtains mixed solution.Then the mixed solution is done under spray drying device with 150 DEG C of temperature
Dry, the pressure for being spray-dried machine nozzle at this time is 0.5MPa, obtains three phosphonitrile of C45, lithium ferric manganese phosphate and ethyoxyl (five fluorine) ring
The NCM622 of three's cladding.
Step 2：Weigh C45 made from 350g steps 1, lithium ferric manganese phosphate and three phosphonitrile three of ethyoxyl (five fluorine) ring cladding
NCM622, in mechanical fusion machine under the rotating speed of 4000rpm merge processing 10min, positive electrode is obtained, with NCM622@A
It indicates.
Embodiment 3
A kind of preparation method of positive electrode, includes the following steps：
Step 1：Three phosphonitrile of NCM622 and pregnancy basic ring is taken, according to mass ratio NCM622:Three phosphonitrile=93 of pregnancy basic ring:7
Ratio be added in N-Methyl pyrrolidone solution and be uniformly dispersed, be sufficiently mixed, obtain mixed solution.Then by the mixing
Solution is dried under spray drying device with 150 DEG C of temperature, and the pressure for being spray-dried machine nozzle at this time is 0.1MPa, is obtained
To the NCM622 of both three phosphonitriles of pregnancy basic ring cladding.
Step 2：The NCM622 that both three phosphonitriles of pregnancy basic ring made from 350g steps 1 coat is weighed, in mechanical fusion machine
In under the rotating speed of 4500rpm merge processing 7min, obtain positive electrode.
Embodiment 4
A kind of preparation method of lithium ion button cell, including following preparation process：
Step 1：Positive electrode, Kynoar obtained by Example 1 and conductive agent, according to mass ratio anode material
Material:Kynoar:Conductive agent=93:3:4 ratio is added in nmp solvent is mixed into slurry through ball grinding stirring, then will
The slurry is coated uniformly on aluminium foil surface, then will be coated with the aluminium foil of slurry successively through roll-in, vacuum at a temperature of 110 DEG C
After dry 12h, anode is obtained；
Step 2：Electric anode, polypropylene micropore diaphragm, lithium piece cathode and electrolyte are assembled into button cell, wherein being electrolysed
Liquid includes ethylene carbonate, methyl ethyl carbonate and six Buddhist phosphoric acid.Ethylene carbonate is 3 with methyl ethyl carbonate volume ratio:7, and contain
There is the LiPF of 1mol/L6。
Embodiment 5
A kind of preparation method of lithium ion button cell, including following preparation process：
Step 1：Positive electrode, Kynoar obtained by Example 2 and conductive agent, according to mass ratio anode material
Material:Kynoar:Conductive agent=93:3:4 ratio is added in nmp solvent is mixed into slurry through ball grinding stirring, then will
The slurry is coated uniformly on aluminium foil surface, then will be coated with the aluminium foil of slurry successively through roll-in, vacuum at a temperature of 110 DEG C
After dry 12h, anode is obtained；
Step 2：Electric anode, polypropylene micropore diaphragm, lithium piece cathode and electrolyte are assembled into button cell, wherein being electrolysed
Liquid includes ethylene carbonate, methyl ethyl carbonate and six Buddhist phosphoric acid.Ethylene carbonate is 3 with methyl ethyl carbonate volume ratio:7, and contain
There is the LiPF of 1mol/L6。
Please refer to Fig.1-Fig. 3 and Fig. 5-Fig. 6.As can be seen from the figure three after spray-dried and mechanofusion method
First material surface forms clad structure.And the combination after mechanofusion method between clad and ternary material becomes more
Step up close.
Effect example
First, at room temperature by the button cell prepared according to 4 method of embodiment as raw material using the positive electrode of embodiment 1
Placement carries out charge-discharge test afterwards for 24 hours, wherein the material after spray drying is sample a, and last positive electrode obtained is sample
b.The voltage of charge and discharge is 2.7-4.35V, and the results are shown in Figure 4.
Secondly, by the button cell prepared according to 4 method of embodiment as raw material using the positive electrode of embodiment 1, to implement
The positive electrode of example 2 is button prepared by the raw material button cell prepared by embodiment 5 and the positive electrode not coated
Battery charges, and button cell is dismantled to and collected after fully charged the dusty material of anode pole piece, using U.S. TA heat
Analyze Q200 instruments carry out differential scanning calorimetry (DSC) test analysis, collect the exothermic peak of each sample starting exothermic temperature,
Peak temperature and thermal discharge Q, the results are shown in Table 1.
Finally, positive electrode pH is tested using national standard GBT 1717-1986 standards, the results are shown in Table 2.
Table 1：There are clad and the not thermal stability of the positive electrode of clad
Table 2：There are clad and not the pH situations of change of the positive electrode of clad
| Sample | NCM523 | NCM523@A | NCM622 | NCM622@A |
| PH value | 11.7 | 10.5 | 11.9 | 10.2 |
First, figure 4, it is seen that when the voltage of charge and discharge is 3.5-4V, the ratio of the sample b after mechanical fusion
Capacity can higher.Therefore mechanical fusion known to us can not only improve the binding force between clad and ternary material, but also
The combination of covering material and ternary material after mechanical fusion in clad obtains even closer so that contact area increases, polarization
Become smaller, finally improves the specific capacity of positive electrode to a certain extent.
Secondly, from fig. 2 it can be seen that the thermal discharge of the positive electrode of embodiment 1 and embodiment 2 with clad is wanted
It is lower with the thermal discharge of the raw material of embodiment 2 than uncoated embodiment 1, and initial temperature and peak temperature want high.Therefore I
It is found that the surface that organic fire-resisting material, inorganic nano material and electrochemical active material are coated to ternary material can be had
Improve the stability of positive electrode in effect ground.
Finally, the pH value of the positive electrode of the embodiment 1 with clad and embodiment 2 is than uncoated embodiment 1
Want low with the pH value of the raw material of embodiment 2.Therefore we are it is found that organic fire-resisting material, inorganic nano material and electrochemistry are lived
The surface that property material is coated to ternary material can be effectively reduced the pH value of material, be conducive to the later stage when preparing button cell
Processing.
The content provided above embodiment of the present invention is described in detail, herein to the principle of the present invention and reality
The mode of applying is expounded and illustrates, the method and its core concept described above for being merely used to help understand the present invention；Meanwhile
For those of ordinary skill in the art, according to the thought of the present invention, has change in specific embodiments and applications
Become place, in conclusion the content of the present specification should not be construed as limiting the invention.
Claims (10)
1. a kind of positive electrode, which is characterized in that including ternary material and the clad for being coated on the ternary material surface, institute
The material for stating clad includes organic fire proofing.
2. positive electrode as described in claim 1, which is characterized in that the material of the clad further includes nano inorganic material
At least one of with electrochemical active material.
3. positive electrode as described in claim 1, which is characterized in that quality of the clad in the positive electrode point
Number is a, wherein 0<A≤20%.
4. positive electrode as described in claim 1, which is characterized in that the organic fire-resisting material includes three phosphonitrile class chemical combination of ring
Object, the cyclotrinitrile phosphide include three phosphonitrile of hexakis-methoxy basic ring, hexaphenoxycyclotriphosphazene, three phosphonitrile of pregnancy basic ring, six
To one or more in three phosphonitrile of aldehyde radical phenoxy cyclotriphosphazene and ethyoxyl (five fluorine) ring.
5. positive electrode as claimed in claim 2, which is characterized in that the nano inorganic material include aluminium oxide, zirconium oxide,
It is one or more in cerium oxide, titanium oxide, barium titanate, silica and conductive carbon black, and/or, the electro-chemical activity material
Material includes that LiFePO4, lithium ferric manganese phosphate, phosphoric acid vanadium lithium, vanadium phosphate oxygen lithium and fluorophosphate vanadium lithium are one or more.
6. positive electrode as claimed in claim 2, which is characterized in that the pH of the positive electrode is 10.0-11.5.
7. positive electrode as described in claim 1, which is characterized in that the material of the clad includes finely dispersed organic
Fire proofing, nano inorganic material and electrochemical active material, the organic fire-resisting material, the nano inorganic material and described
Mass fraction of the electrochemical active material in the positive electrode is respectively b, c and d, wherein 0<B≤2%, 0<C≤16%,
0<D≤2%.
8. a kind of preparation method of positive electrode, which is characterized in that include the following steps：
Ternary material is taken, the ternary material is sufficiently mixed in a solvent with covering material, obtains mixed solution, the cladding
Material includes organic fire proofing；
It carries out mechanical fusion after the mixed solution is spray-dried, obtains the ternary material of clad cladding, i.e., it is positive
Material.
9. preparation method as claimed in claim 8, which is characterized in that the covering material further includes nano inorganic material and electricity
At least one of chemically active material, the preparation method specifically include following steps：
Ternary material is taken, by least one of nano inorganic material and electrochemical active material and the ternary material and institute
It states organic fire-resisting material to be sufficiently mixed in a solvent, obtains mixed solution, carried out after the mixed solution is spray-dried
Mechanical fusion obtains positive electrode.
10. preparation method as claimed in claim 8, which is characterized in that the temperature of the spray drying is 80-250 DEG C, and/
Or, the rotating speed of the mechanical fusion is 3000-5500rpm, the time of the mechanical fusion is 3-20min.
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