CN106099047A - A kind of surface coating method of electrode material and application thereof - Google Patents
A kind of surface coating method of electrode material and application thereof Download PDFInfo
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- CN106099047A CN106099047A CN201610723465.9A CN201610723465A CN106099047A CN 106099047 A CN106099047 A CN 106099047A CN 201610723465 A CN201610723465 A CN 201610723465A CN 106099047 A CN106099047 A CN 106099047A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides method for coating of a kind of electrode material and application thereof, the method for the present invention comprises the following steps: (1) grows metallic organic framework at the surface in situ of electrode material；(2) electrode material of the metallic organic framework cladding obtained is carried out heat treatment, obtain oxide jacketed electrode material.The present invention has the metal-organic framework materials of suitable appearance and size and object ion metal cluster as presoma by design, it is converted into nano-oxide after heat treatment, it is possible not only to realize metal-oxide in the effectively cladding of electrode material surface, regulation and control to metal oxide structures and covering amount thereof, may be incorporated into Surface coating material and structure that more traditional method is difficult to, be a kind of novel electrode material surface cladding means.
Description
Technical field
The invention belongs to electrode material preparation and technical field of lithium ion, relate to the Surface coating of a kind of electrode material
Method and application thereof, a kind of surface coated method particularly relating to electrode material, the oxide using the method to prepare
Jacketed electrode material, and comprise the lithium ion battery of this oxide jacketed electrode material.
Background technology
Lithium ion battery because having a high energy density, the advantage such as excellent cycle performance and stable running voltage,
The most extensively quoted at present.The demand of lithium ion battery applications is also constantly being expanded by market, traditional consumption electronic product,
Peak load regulation network energy storage, start and stop power supply, the specific energy of lithium ion battery and cycle performance are all proposed more by electric automobile etc. field
High request.Material surface cladding is the important method of business-like anode material for lithium-ion batteries application enhancements, and cladding can reach
To suppression surface erosion, protecting material structure, it is achieved the purpose of stable circulation, the most extensively method for coating includes solid phase mixing,
Vapour deposition, conventional physical, the chemical method such as liquid-phase precipitation, by novel method for coating and thinking, and then reach more preferable
The freshest rare all reports of covered effect.
But current method for coating generally also exists electrode material surface occurs what side reaction and surface erosion destroyed
Problem, thus it is necessary to research and develop a kind of novel surface coating method to solve described problem present in prior art.
In the twenty or thirty year in past, metal-organic framework materials (MOF) is due to the structure of its grace and changeable chemistry
Character, is obtained at a lot of aspects such as gas storage, ion exchange, molecule separation and diversified catalysis and widely should
With.Therefore, MOF material grinds to make internal disorder or usurp conveniently there has also been huge development in design, synthesis and feature, and also cause MOF material enters one
Step deeply development.These solid materials are combined with metal cluster by organic bridge part (or being called " support ") and form three-dimensional
Extension network structure, this series material specific surface area can arrive 7000m2/ g, people can set the most effectively
The aperture of meter regulation material and specific surface area.Metal cluster typically has one or more metal ions (such as Al3+, Mg2+, Cr3+,
Ti4+, Zn2+And Zr4+Deng) constitute, metals is linked by specific functional group (such as carboxylic acid, pyridine etc.) with organic bridge part.
The most thousands of kinds of MOF materials of research report.Metallic organic framework is used for jacketed electrode material and prepares high-quality
Jacketed electrode material there are important research and development be worth.
Summary of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of novel electrode material
Surface coating modification method, described method for coating has novelty, practical, and can introduce big on the surface of electrode material
Most metal-oxides are to realize cladding, and metal-oxide grows equably and is coated on electrode material, and clad is at nanoscale, bag
Cover effective, have broad application prospects.
For reaching above-mentioned purpose, the present invention by the following technical solutions:
First aspect, the present invention provides the surface coating method of a kind of electrode material, said method comprising the steps of:
(1) surface in situ at electrode material grows metallic organic framework, obtains the electrode material of metallic organic framework cladding
Material；
(2) electrode material of metallic organic framework cladding is carried out heat treatment, obtain oxide jacketed electrode material.
Electrode material of the present invention can be positive electrode, it is also possible to be negative material.Preferably include polyanionic
Positive electrode LiMXOδAnd/or transition metal oxide LiNσOλ, wherein, M be in Fe, Mn, Co or Ni any one or at least
The combination of two kinds；X is any one or the combination of at least two in P, B, Si or S；1≤δ≤5；N is Co, Mn, Ni, Al,
Any one or the combination of at least two in Mg, Fe, Zn, Cr, V, Ti, Zr or Ru；0.5≤σ≤4.0；1≤λ≤5.But also
Being not limited to the above-mentioned electrode material enumerated, other electrode materials commonly used in the art can also be used for the present invention.
Electrode material of the present invention can use method disclosed in prior art to prepare, and is preferably without cladding
Or the electrode material of modification.
In the present invention, described " surface in situ at electrode material grows metallic organic framework " can realize single component metal
Organic backbone jacketed electrode material；Multicomponent metallic organic framework jacketed electrode material can also be realized.Thus, warp further
Follow-up heat treatment can realize one pack system or multi-component metal oxide jacketed electrode material.
Metallic organic framework in the present invention can be the one in various metals organic backbone commonly used in the art or extremely
The combination of few two kinds, such as, can be that Al Base Metal organic backbone (such as MIL-53 etc.), Mg Base Metal organic backbone are (such as Mg-
MOF-74 etc.), Ti Base Metal organic backbone (such as MIL-125 etc.), Zn Base Metal organic backbone (such as ZIF-8 etc.), Co Base Metal
Organic backbone (such as Co-ZIF-9 etc.), V Base Metal organic backbone (such as MIL-47), Cr/Fe Base Metal organic backbone are (such as MIL-
100 (Fe, Cr) etc.), in Zr Base Metal organic backbone (such as UiO-68 etc.) or Ni Base Metal organic backbone (such as MOF-74 etc.)
Any one or the mixture of at least two, but it is not limited to the above-mentioned metallic organic framework enumerated, the present invention can use greatly
The metallic framework material of most metallic element respective metal bunch as presoma, thus, the oxide jacketed electrode finally given
The kind of the metal-oxide clad in material is the most diversified, reaches excellent Surface coating effect.
Heretofore described " P Base Metal organic backbone (any one in P=Al, Mg, Ti, Zn, Co, V, Zr or Ni
Kind) " refer to: the metal P ion containing only single kind of the metal cluster in this metallic organic framework, illustrate, as P=Al, should
The metal cluster in the metallic organic framework metallic aluminium ion containing only single kind.
It is heretofore described that " Cr/Fe Base Metal organic backbone refers to: the metal cluster in this metallic organic framework contains two kinds
Metal ion, i.e. chromium ion and iron ion.
In the present invention, metal-organic framework materials prepares coating in oxide jacketed electrode material as the present invention
Presoma, continues through heat treatment mode and can be changed into metal-oxide and be coated on the surface of electrode material.
Preferably, step (1) in the method for the surface in situ growth metallic organic framework of electrode material is:
Make the mixed liquor comprising electrode material, slaine and chelating agent react, obtain metallic organic framework cladding
Electrode material.
In above-mentioned reaction, slaine and chelating agent react and generate metallic organic framework and be coated to the table of electrode material
Face.
Step of the present invention (1) is in the surface in situ of electrode material grows the method for metallic organic framework, and preparation comprises electricity
During the mixed liquor of pole material, slaine and chelating agent, the addition sequence of each raw material is not limited, such as, can use following several
The scheme of kind: 1. electrode material is distributed in solvent I, obtains dispersion liquid X1；In dissolving metal salts to solvent II, mixed
Liquid Y1；Chelating agent is distributed in solvent III, obtains mixed liquor Z1；Then, dispersion liquid X1, mixed liquor Y1 and mixed liquor Z1 are mixed
Close, obtain mixed liquor.2. electrode material is distributed in solvent I, obtains dispersion liquid X2；Slaine and chelating agent are joined
State in dispersion liquid X2, obtain mixed liquor.3., dissolving metal salts in solvent I, mixed liquor X3 is obtained；Electrode material is joined
In above-mentioned mixed liquor X3, obtain dispersion liquid Y3；Chelating agent is dissolved in solvent II, obtains mixed liquor Z3；By dispersion liquid Y3 and
Mixed liquor Z3 mixes, and obtains mixed liquor.4. slaine and chelating agent are dissolved in solvent I, obtain mixed liquor X4；To above-mentioned mixed
Close and liquid X4 adds electrode material, obtain mixed liquor.5. slaine is dissolved in solvent I, obtains mixed liquor X5；Chelating agent is molten
Solution, in solvent II, obtains mixed liquor Y5；Mixed liquor X5 and mixed liquor Y5 is mixed, obtains mixed liquor Z5；To above-mentioned mixed liquor
Z5 adds electrode material, obtains mixed liquor.
Heretofore described solvent I, II and III is all independently selected from methanol, ethanol, benzene, DMF (N, N-
Dimethylformamide, dimethylformamide), DNF or NMP (N-methyl-2-pyrrolidone, N-crassitude
Ketone) in any one or the mixture of at least two, but be not limited to the above-mentioned organic solvent enumerated, for some electrode material
The Surface coating of material, also can add water in solvent during cladding.
Thus, it is known that, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, institute
Stating the solvent in mixed liquor is any one or the mixture of at least two in methanol, ethanol, benzene, DMF, DNF or NMP, but
It is not limited to the above-mentioned organic solvent enumerated, it is also possible to include water.
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, also includes
Organic solvent is carried out except the step of water before organic solvent uses.
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described electricity
Pole material includes polyanionic positive electrode LiMXOδAnd/or transition metal oxide LiNσOλ；Wherein, M be Fe, Mn, Co or
Any one or the combination of at least two in Ni；X is any one or the combination of at least two in P, B, Si or S；1≤δ
≤5；N is any one or the combination of at least two in Co, Mn, Ni, Al, Mg, Fe, Zn, Cr, V, Ti, Zr or Ru；0.5≤σ
≤4.0；1≤λ≤5；
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described gold
Belong to salt include the sulfate of nickel, cobalt, aluminum, magnesium, chromium and titanium, nitrate and chloride, in any one or at least two mixed
Compound, such as nickel sulfate, nickel nitrate, Nickel dichloride., cobaltous sulfate, cobalt nitrate, cobaltous chloride, aluminum sulfate, aluminum nitrate, aluminum chloride, sulphuric acid
In magnesium, magnesium nitrate, magnesium chloride, chromic sulfate, chromic nitrate, Chlorizate chromium, titanium sulfate, Titanium Nitrate and titanium chloride any one or at least
The mixture of two kinds, but it is not limited to the above-mentioned slaine enumerated, the metal that metallic organic framework is conventional is prepared in other this areas
Salt can also be used for the present invention.
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described network
Mixture includes any one or the mixture of at least two in carboxylic acid, pyridine or pyrazine, but is not limited to the above-mentioned network enumerated
Mixture, other chelating agent commonly used in the art can also be used for the present invention.It is preferably formic acid, p-phthalic acid, trimesic acid, connection
Any one or the mixture of at least two in pyridine or pyrazine.
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described gold
The mass ratio belonging to salt and chelating agent is 1:1～1:20, can be such as 1:1,1:2,1:3,1:4,1:5,1:6,1:7,1:7.5,1:
8,1:10,1:11,1:12,1:14,1:15,1:16,1:17,1:18 or 1:20 etc..
In step of the present invention (1), slaine and the ratio of electrode material, directly determine the oxide cladding finally given
The covering amount of the metal-oxide in electrode material.By slaine synthesis metal-organic framework materials productivity at 50-100% based on
Calculate, be converted into covering amount relation, the mass ratio of the final metal-oxide in oxide jacketed electrode material and matrix 0～
20%, and do not include 0, can be such as 0.5%, 1%, 3%, 5%, 10%, 13%, 15% or 20% etc..
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described mixed
Closing in liquid and also include accessory molecule, accessory molecule is for controlling generation and the crystallization rate of metal-organic framework materials.Described auxiliary
Molecule is helped to be preferably lewis base, more preferably triethylamine.
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described instead
Should be in room temperature reaction, hydro-thermal reaction or solvent thermal reaction any one.
In the present invention, described room temperature refers to 15～38 DEG C, can be such as 15 DEG C, 18 DEG C, 20 DEG C, 23 DEG C, 25 DEG C, 28 DEG C, 30
DEG C, 32 DEG C, 35 DEG C or 38 DEG C etc..
Preferably, the temperature of described reaction room temperature～200 DEG C, can be such as 15 DEG C, 20 DEG C, 25 DEG C, 28 DEG C, 30 DEG C,
35℃、40℃、45℃、50℃、60℃、65℃、75℃、80℃、90℃、100℃、110℃、120℃、130℃、150℃、
160 DEG C, 170 DEG C, 185 DEG C or 200 DEG C etc., preferably 80～200 DEG C.
In the present invention, described room temperature reaction refers to: make mixed liquor react at ambient temperature, without heating or the fall of auxiliary
Temperature device (being not related to heating process and hydro-thermal reaction etc.).
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described instead
The time answered is 0.5-72h, can be such as 0.5h, 1h, 1.3h, 2h, 3h, 3.5h, 4h, 5h, 6h, 8h, 10h, 12h, 15h,
18h, 20h, 24h, 28h, 32h, 36h, 38h, 40h, 42h, 45h, 50h, 52h, 56h, 60h, 62h, 67h, 70h or 72h etc., excellent
Elect 24～72h as.
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, also includes
After completion of the reaction, the step separating, clean and drying is carried out.
In the present invention, described separation can use the separation means well known in the art such as filtration, centrifugal and extraction.
In the present invention, material dry before also need to sufficiently wash, described washing use solvent be methanol,
Any one or the mixture of at least two in ethanol, benzene, DMF, DNF, NMP or water.
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described baking
Dry temperature is 50～200 DEG C, can be such as 50 DEG C, 70 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 130 DEG C, 150 DEG C, 160 DEG C, 180
DEG C or 200 DEG C etc., be dried in this temperature range, both can remove ligand molecular and impurity salt, can keep again simultaneously
Stablizing of metal-organic framework materials.
Preferably, the temperature of step (2) described heat treatment is 200～900 DEG C, can be such as 200 DEG C, 300 DEG C, 350 DEG C,
400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 620 DEG C, 650 DEG C, 670 DEG C, 720 DEG C, 760 DEG C, 800 DEG C, 850 DEG C or 900
DEG C etc..
Preferably, the time of step (2) described heat treatment is 0.5～10h, can be such as 0.5h, 1h, 1.5h, 1.8h,
2h, 3h, 3.5h, 4h, 4.5h, 4.8h, 5h, 6h, 6.5h, 7h, 7.3h, 7.6h, 8h, 8.5h, 9h or 10h etc..
Preferably, step (2) described heat treatment is carried out under atmosphere, and described atmosphere is oxygen atmosphere, air
Which kind of atmosphere any one or the combination of at least two in atmosphere or inert atmosphere, concrete select need to be according to heat treatment
Temperature and matrix material and the kind of metallic organic framework and determine, such as, when LiFePO 4 material is carried out Surface coating
Use inert atmosphere；When LiMn2O4 and ternary material are coated with, use oxygen atmosphere or air atmosphere.
Preferably, during described inert atmosphere is nitrogen atmosphere, helium atmosphere, neon atmosphere, argon gas atmosphere or Krypton atmosphere
Any one or the combination of at least two.
As the optimal technical scheme of method for coating of the present invention, the surface coating method of a kind of electrode material, described
Method comprises the following steps:
(1) make the mixed liquor reaction 0.5-72h comprising electrode material, slaine and chelating agent, carried out after having reacted
Filter, cleaning are also dried in 50～200 DEG C, obtain the electrode material of metallic organic framework cladding；
(2) by metallic organic framework be coated with electrode material in 200～900 DEG C in atmosphere heat treatment 0.5～
10h, obtains oxide jacketed electrode material.
Second aspect, the present invention provides the purposes of a kind of surface coating method as above.
One of described purposes prepares oxide jacketed electrode material, described oxide cladding electricity for using above-mentioned method for coating
Pole material comprises electrode material and is coated on the metal-oxide clad of electrode material surface.
Preferably, to be that the metallic organic framework by step (1) is thermally treated be transformed described metal-oxide clad
, the kind of the chemical analysis of metal-oxide clad is corresponding with the kind of metallic organic framework, when the organic bone of metal
When frame is Al Base Metal organic backbone, the chemical analysis of the metal-oxide clad being correspondingly made available is aluminium oxide；Work as metal
When organic backbone is Mg Base Metal organic backbone, the chemical analysis of the metal-oxide being correspondingly made available is magnesium oxide；Work as metal
When organic backbone is Cr/Fe Base Metal organic backbone, the chemical analysis of the metal-oxide being correspondingly made available is chromium oxide and oxygen
Change the mixture of ferrum.
In like manner understanding, the chemical analysis of the metal-oxide in the oxide jacketed electrode material of the present invention includes oxidation
Any one in aluminum, magnesium oxide, titanium oxide, zinc oxide, cobalt oxide, vanadium oxide, chromium oxide, ferrum oxide, zirconium oxide or nickel oxide
Plant or the combination of at least two.But it is not limited to the above-mentioned metal-oxide enumerated, when using other metals commonly used in the art
Organic backbone when the present invention, then can get corresponding metal-oxide.
The present invention can by regulation and control the kind of metallic organic framework, pattern, size, hole, degree of crystallinity, specific surface area and
The parameters such as addition, it is achieved the regulation and control to the composition of metal-oxide, structure and the covering amount thereof of final cladding.Such as, when
During covering amount the lowest (content of metal-oxide the most therein is the lowest) of the oxide jacketed electrode material obtained eventually, preferably adopt
With there is the easily controllable metallic organic framework of macromolecule, bigger serface and crystal growth as presoma, warp further
Heat treatment is converted into metal-oxide, thus realizes preferable covered effect more accurately and reliably.
Preferably, described metal-oxide clad is 0～20% with the mass ratio of matrix material, and does not include 0%, matter
Amount ratio as can be 0.1%, 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 7%, 10%, 12%, 15%, 18%,
19% or 20% etc., preferably 0.25～10%.
The two of described purposes are for providing a kind of lithium ion battery comprising above-mentioned jacketed electrode material.
Compared with prior art, there is advantages that
(1) present invention is by having at the surface in situ growth metal of electrode material matrix using organic facies as primary response system
Machine skeleton, is then converted into uniform thin oxide layer by heat treatment by the metallic organic framework clad on surface, obtains oxygen
Compound jacketed electrode.The method of the present invention can not only make covering material be grown on base matter, and is capable of preferably
In conjunction with and covered effect, be conducive to introducing Surface coating material and structure that more tradition method for coating is difficult to simultaneously, be
A kind of novel and preferable coating technology.
(2) present invention can be by the regulation and control kind of metallic organic framework, pattern, size, hole, degree of crystallinity, specific surface
The parameters such as long-pending and addition, it is achieved metal-oxide and the regulation and control of covering amount thereof to final cladding, to realize preferably cladding
Effect.
(3) battery is made using the oxide jacketed electrode material of the present invention as the positive electrode of lithium ion battery, performance
Going out extraordinary cycle performance, normal temperature condition 1C constant current charge-discharge 40 weeks, capability retention was up to 97.5%, compared to cladding
Electrode material before, capability retention improves up to 5.57 percentage points.
Accompanying drawing explanation
Fig. 1 is the mechanism explanation schematic diagram that the present invention prepares oxide jacketed electrode material, and wherein, 1 represents electrode material；
2 represent metallic organic framework；3 represent metal-oxide clad；
Fig. 2 be the present invention implement 1 and comparative example 1 prepared by positive electrode make the cycle performance correlation curve of battery,
Wherein, matrix material represents the positive electrode of comparative example 1 preparation；Covering material represents the positive electrode of embodiment 1 preparation.
Detailed description of the invention
Further illustrate technical scheme below in conjunction with the accompanying drawings and by detailed description of the invention.
Use following methods to embodiment 1～6 and the positive electrode of comparative example 1 test:
Use following methods test electrochemistry cycle performance: by positive electrode, conductive agent and binding agent by mass percentage
They are dissolved and mix in a solvent by 90:5:5, and control solid content, 50%, is coated in aluminum foil current collector, vacuum drying, system
Obtain anode pole piece.The charge-discharge test of button cell on Xin Wei Electronics Co., Ltd. of Shenzhen neware battery test system,
At normal temperature condition, 0.2C constant current charge-discharge 3 weeks, then the rate charge-discharge 40 weeks with 1C, charging/discharging voltage be limited in 2.75～
4.3V。
Embodiment 1
(1) use coprecipitation method synthesis nickelic NCM (Ni:Co:Mn=8:1:1) presoma, compare by Li/ (Ni+Co+Mn)
Example 1.05 mixes lithium source (LiOH), obtains electrode material LiNi after sintered process0.8Co0.1Mn0.1O2As matrix, by this base
Body material carries out crushing, sieving and dried before cladding, collects standby.
(2), after weighing DMF, methanol 1:1 by volume mixing respectively, it is made into homogeneous solvent, by 20g electrode material
LiNi0.8Co0.1Mn0.1O2Joining in above-mentioned homogeneous solvent, dispersed with stirring is uniform, obtains disperse system.
(3) weigh cobalt nitrate 0.36g and p-phthalic acid 0.075g respectively, and add it to that step (2) obtains point
Dissipate in system, ultrasonic 30min, obtain mixed liquor, wherein cobalt nitrate and p-phthalic acid mol ratio are 3:1.
(4) proceed to, in water heating kettle, tighten sealing by the mixed liquor of step (3), at 100 DEG C in thermostat water bath, stir water
Thermal response 10h, takes out after being then cooled to room temperature, changes the solution in water heating kettle with methanol；Then sealing is tightened, at 100 DEG C
In thermostat water bath, stirring hydro-thermal reaction 10h, so circulation 3 times, i.e. stirs the total reaction time about 30h of hydro-thermal reaction.
(5) after completing above step, product vacuum drying at 100 DEG C that step (4) is obtained, it is then charged into crucible,
Put chamber type electric resistance furnace into, at 500 DEG C, heat treatment 5h under oxygen atmosphere, obtain cobalt oxide cladding after cooling
LiNi0.8Co0.1Mn0.1O2。
The positive electrode of the present embodiment 1 and comparative example 1 preparation makes battery, and its cycle performance curve is shown in Fig. 1, can by figure
Knowing, positive electrode has had be obviously improved in cladding Posterior circle performance, compared to the electrode material (comparative example 1) before cladding, and 40 weeks
Conservation rate is promoted to 96.0% by 90.9%, illustrates that this method for coating has directly effect to material stablizing in cyclic process.
Embodiment 2
(1) coprecipitation method synthesis nickelic NCA (Ni:Co:Al=0.815:0.15:0.035) presoma is used, by Li/
(Ni+Co+Al) ratio 1.03 mixes lithium source (LiOH), obtains electrode material LiNi after sintered process0.15Co0.15Al0.035O2Make
For matrix, carry out this matrix material crushing, sieving and dried before cladding, collect standby.
(2) measure methanol 250mL, and weighing magnesium nitrate 1.4g, join in methanol, be sufficiently stirred for dissolving and obtain solution,
Weigh 100g electrode material LiNi0.15Co0.15Al0.035O2Join in above-mentioned solution, fully dispersed, obtain disperse system I；
(3) separately measure methanol 250mL, be added thereto to 3g formic acid, after being thoroughly mixed uniformly, obtain disperse system II.
(4) disperse system I and disperse system II are poured in reactor and mix, add 3g triethylamine, shake up, seal, under room temperature
Standing 24h, reaction takes out mixed stocker after terminating, and with methanol as solvent, after centrifugation repeatedly, obtains cleaning product.
(5) after completing above step, product vacuum drying at 100 DEG C that step (4) is obtained, it is then charged into crucible,
Put chamber type electric resistance furnace into, at 400 DEG C, heat treatment 4h under oxygen atmosphere, obtain magnesium oxide cladding after cooling
LiNi0.15Co0.15Al0.035O2。
Prepared by the present embodiment makes battery as positive electrode, compared to the electrode material (comparative example 2) before cladding, its
Cycle performance cladding Posterior circle performance has had and has been obviously improved, and within 40 weeks, conservation rate is promoted to 93.3% by 88.1%.
Embodiment 3
(1) use coprecipitation method synthesis nickelic NCM (Ni:Co:Mn=6:2:2) presoma, compare by Li/ (Ni+Co+Mn)
Example 1.08 mixes lithium source (LiOH), obtains electrode material LiNi after sintered process0.6Co0.2Mn0.2O2As matrix.
(2) in politef reactor, ANN aluminium nitrate nonahydrate 400mg, trimesic acid 300mg, sodium hydroxide are added
200mg, and deionized water 10mL, be stirred until homogeneous, obtain disperse system.
(3) in described disperse system, 100g electrode material LiNi is added0.6Co0.2Mn0.2O2, fully dispersed uniformly, mixed
Close liquid.
(4) mixed liquor of step (3) is loaded reactor and move into 150 DEG C of baking ovens, react 48h, take out after cooling, through methanol
Solvent is centrifugally separating to obtain product presoma.
(5) after completing above-mentioned steps, product presoma vacuum drying at 100 DEG C that step (4) is obtained, it is then charged into
Crucible, puts chamber type electric resistance furnace into, at 650 DEG C, and heat treatment 5h under oxygen atmosphere, obtain alumina-coated after cooling
LiNi0.6Co0.2Mn0.2O2。
Prepared by the present embodiment makes battery as positive electrode, compared to the electrode material (comparative example 3) before cladding, its
Cycle performance cladding Posterior circle performance has had and has been obviously improved, and within 40 weeks, conservation rate is promoted to 95.3% by 92.5%.
Embodiment 4
(1) use iron phosphate as presoma, be 1.02 mixing lithium sources in Li/Fe ratio, wherein lithium source be LiOH with
Li2CO3In 97:3 ratio, after mix homogeneously, through the lower 680 DEG C of sintering 12h of nitrogen atmosphere, obtain electrode material LiFePO4As base
Body.
(2) 2.4g p-phthalic acid is joined wiring solution-forming I in 7.5g DMF, 1.7g nine water and aluminum nitrate are joined
Wiring solution-forming II in 7.5g DMF, mixes solution I and solution II, stirs.
(3) 100g electrode material LiFePO is then weighed4, join step (2) be made up of solution I and solution II mixed
Close in solution, obtain mixed liquor.
(4) it is sufficiently stirred for the mixed liquor of step (3) at 130 DEG C reacting 24h.Then solid is leached, abundant with methanol
Washing.
(5), after completing above step, product step (4) obtained is in 100 DEG C of vacuum oven, then by above-mentioned
Solid loads crucible, puts chamber type electric resistance furnace into, at 500 DEG C, and heat treatment 10h under oxygen atmosphere, obtain alumina-coated after cooling
LiFePO4。
Prepared by the present embodiment makes battery as positive electrode, compared to the electrode material (comparative example 4) before cladding, its
Cycle performance cladding Posterior circle performance has had and has been obviously improved, and within 40 weeks, conservation rate is promoted to 97.5% by 95.2%.
Embodiment 5
(1) use coprecipitation method synthesis nickelic NCM (Ni:Co:Mn=5:2:5) presoma, compare by Li/ (Ni+Co+Mn)
Example 1.08 mixes lithium source (LiOH), obtains electrode material LiNi after sintered process0.5Co0.2Mn0.3O2As matrix.
(2) measure DMF 150mL, be added thereto to 1g Aluminium chloride hexahydrate and 0.45g ZrOCl2, it is configured to solution I；
Measure DMF 150mL again, add 1.63g p-phthalic acid, be configured to solution II, solution I and solution II mixed, stirs evenly.
(3) in the mixed solution being made up of solution I and solution II, 100g electrode material LiNi is added0.5Co0.2Mn0.3O2,
Obtain mixed liquor.
(4) it is sufficiently stirred for the mixed liquor of step (3) reacting 17h under the conditions of 150 DEG C of oil baths, then leaches solid, use
After methanol washing.
(5) after completing above step, the product that step (4) is obtained in vacuum drying oven 100 DEG C be dried overnight.Then will
Above-mentioned solid load crucible, put chamber type electric resistance furnace into, at 350 DEG C, heat treatment 8h under oxygen atmosphere, obtain after cooling aluminium oxide and
The LiNi of zirconium oxide cladding0.5Co0.2Mn0.3O2。
Prepared by the present embodiment makes battery as positive electrode, compared to the electrode material (comparative example 5) before cladding, its
Cycle performance cladding Posterior circle performance has had and has been obviously improved, and within 40 weeks, conservation rate is promoted to 96.8% by 94.1%.
Embodiment 6
(1) use coprecipitation method synthesis nickelic NCM (Ni:Co:Mn=1:1:1) presoma, compare by Li/ (Ni+Co+Mn)
Example 1.08 mixes lithium source (LiOH), obtains electrode material LiNi after sintered process1/3Co1/3Mn1/3O2As matrix.
(2) measure DMF 30mL, be added thereto to four acetate hydrate cobalt 2.70g, after dissolving, another addition 50g electrode material
LiNi1/3Co1/3Mn1/3O2, it is uniformly mixed, obtains disperse system I.
(3) measuring DMF 30mL again, be added thereto to p-phthalic acid 1.5g, dissolving postscript is disperse system II, will dispersion
Be I and disperse system II be sufficiently mixed, stir, obtain mixed liquor.
(4) mixed liquor of step (3) is transferred to teflon-lined autoclave seal, wherein adds magnetic force
Stirrer, after sealing, continuously stirred reaction in oil bath pan, reaction temperature is 140 DEG C, and the response time is 72h, and reaction terminates cold
But, after, it is centrifugally separating to obtain solid.
(5), after completing above-mentioned steps, solid step (4) obtained loads crucible, puts chamber type electric resistance furnace into, at 450 DEG C,
Heat treatment 5h under oxygen atmosphere, obtains the LiNi of cobalt oxide cladding after cooling1/3Co1/3Mn1/3O2。
Prepared by the present embodiment makes battery as positive electrode, compared to the electrode material (comparative example 6) before cladding, its
Cycle performance cladding Posterior circle performance has had and has been obviously improved, and within 40 weeks, conservation rate is promoted to 95.3% by 93.8%.
Embodiment of the present invention 1-6 is prepared the mechanism explanation schematic diagram of oxide jacketed electrode material and is seen Fig. 1.
Comparative example 1
The method identical with embodiment 1 step (1) and condition is used to prepare electrode material LiNi0.8Co0.1Mn0.1O2。
This comparative example does not adds slaine, thus without the generation of metallic organic framework, without gold in the product finally given
Belong to oxide cladding layers.Electrode material prepared by this comparative example, as positive pole, uses method same as in Example 1 to make electricity
Pond, detects under the same terms, and within 40 weeks, conservation rate is 90.9%.
Comparative example 2
The method identical with embodiment 2 step (1) and condition is used to prepare electrode material LiNi0.15Co0.15Al0.035O2。
This comparative example does not adds slaine, thus without the generation of metallic organic framework, without gold in the product finally given
Belong to oxide cladding layers.Electrode material prepared by this comparative example, as positive pole, uses method same as in Example 2 to make electricity
Pond, detects under the same terms, and within 40 weeks, conservation rate is 88.1%.
Comparative example 3
The method identical with embodiment 3 step (1) and condition is used to prepare electrode material LiNi0.6Co0.2Mn0.2O2。
This comparative example does not adds slaine, thus without the generation of metallic organic framework, without gold in the product finally given
Belong to oxide cladding layers.Electrode material prepared by this comparative example, as positive pole, uses method same as in Example 3 to make electricity
Pond, detects under the same terms, and within 40 weeks, conservation rate is 92.5%.
Comparative example 4
The method identical with embodiment 4 step (1) and condition is used to prepare electrode material LiFePO4。
This comparative example does not adds slaine, thus without the generation of metallic organic framework, without gold in the product finally given
Belong to oxide cladding layers.Electrode material prepared by this comparative example, as positive pole, uses method the same as in Example 4 to make electricity
Pond, detects under the same terms, and within 40 weeks, conservation rate is 95.2%.
Comparative example 5
The method identical with embodiment 5 step (1) and condition is used to prepare electrode material LiNi0.5Co0.2Mn0.3O2。
This comparative example does not adds slaine, thus without the generation of metallic organic framework, without gold in the product finally given
Belong to oxide cladding layers.Electrode material prepared by this comparative example, as positive pole, uses method same as in Example 5 to make electricity
Pond, detects under the same terms, and within 40 weeks, conservation rate is 94.1%.
Comparative example 6
The method identical with embodiment 6 step (1) and condition is used to prepare electrode material LiNi1/3Co1/3Mn1/3O2。
This comparative example does not adds slaine, thus without the generation of metallic organic framework, without gold in the product finally given
Belong to oxide cladding layers.Electrode material prepared by this comparative example, as positive pole, uses method same as in Example 6 to make electricity
Pond, detects under the same terms, and within 40 weeks, conservation rate is 93.8%.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. the surface coating method of an electrode material, it is characterised in that said method comprising the steps of:
(1) surface in situ at electrode material grows metallic organic framework, obtains the electrode material of metallic organic framework cladding；
(2) electrode material of metallic organic framework cladding is carried out heat treatment, obtain oxide jacketed electrode material.
Method for coating the most according to claim 1, it is characterised in that described electrode material includes polyanionic positive pole material
Material LiMXOδAnd/or transition metal oxide LiNσOλ；
Wherein, any one or the combination of at least two during M is Fe, Mn, Co or Ni；X is any one in P, B, Si or S
Or the combination of at least two；1≤δ≤5；
N is any one or the combination of at least two in Co, Mn, Ni, Al, Mg, Fe, Zn, Cr, V, Ti, Zr or Ru；0.5≤σ
≤4.0；1≤λ≤5；
Preferably, described metallic organic framework includes that Al Base Metal organic backbone, Mg Base Metal organic backbone, Ti Base Metal are organic
Skeleton, Zn Base Metal organic backbone, Co Base Metal organic backbone, V Base Metal organic backbone, Cr/Fe Base Metal organic backbone, Zr
Any one or the mixture of at least two in Base Metal organic backbone or Ni Base Metal organic backbone.
Method for coating the most according to claim 1 and 2, it is characterised in that step (1) is described former on the surface of electrode material
The method of position growth metallic organic framework is:
Make the mixed liquor comprising electrode material, slaine and chelating agent react, obtain the electrode of metallic organic framework cladding
Material.
Method for coating the most according to claim 3, it is characterised in that the described surface in situ at electrode material of step (1)
In the method for growth metallic organic framework, described electrode material includes polyanionic positive electrode LiMXOδAnd/or transition gold
Belong to oxide LiNσOλ；Wherein, any one or the combination of at least two during M is Fe, Mn, Co or Ni；X is in P, B, Si or S
Any one or the combination of at least two；1≤δ≤5；N is in Co, Mn, Ni, Al, Mg, Fe, Zn, Cr, V, Ti, Zr or Ru
Any one or the combination of at least two；0.5≤σ≤4.0；1≤λ≤5；
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described slaine
Including any one in sulfate, nitrate and the chloride of nickel, cobalt, aluminum, magnesium, chromium and titanium or the mixture of at least two；
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described chelating agent
Including any one in carboxylic acid, pyridine or pyrazine or the mixture of at least two, preferably formic acid, p-phthalic acid, equal benzene
Any one or the mixture of at least two in tricarboxylic acid, bipyridyl or pyrazine；
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described slaine
It is 1:1～1:20 with the ratio of the amount of chelating agent material.
5. according to the method for coating described in claim 3 or 4, it is characterised in that step (1) is described former on the surface of electrode material
In the method for position growth metallic organic framework, the solvent in described mixed liquor is in methanol, ethanol, benzene, DMF, DNF or NMP
Any one or the mixture of at least two；
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described mixed liquor
In also include that accessory molecule, described accessory molecule are preferably lewis base, more preferably triethylamine.
6. according to the method for coating described in any one of claim 3-5, it is characterised in that step (1) is described at electrode material
In the method for surface in situ growth metallic organic framework, described reaction is in room temperature reaction, hydro-thermal reaction or solvent thermal reaction
Any one；
Preferably, the temperature of described reaction room temperature～200 DEG C, preferably 80～200 DEG C；
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described reaction
Time is 0.5-72h, preferably 24～72h.
7. according to the method for coating described in any one of claim 3-6, it is characterised in that step (1) is described at electrode material
In the method for surface in situ growth metallic organic framework, it is additionally included in after reaction completes, carries out the step separating, clean and drying
Suddenly；
Preferably, the described surface in situ at electrode material of step (1) grows in the method for metallic organic framework, described drying
Temperature is 50～200 DEG C.
8. according to part method for coating described in any one of claim 1-7, it is characterised in that the temperature of step (2) described heat treatment
It it is 200～900 DEG C；
Preferably, the time of step (2) described heat treatment is 0.5～10h；
Preferably, step (2) described heat treatment is carried out under atmosphere, and described atmosphere is oxygen atmosphere, air atmosphere
Or any one or the combination of at least two in inert atmosphere；
Preferably, appointing during described inert atmosphere is nitrogen atmosphere, helium atmosphere, neon atmosphere, argon gas atmosphere or Krypton atmosphere
Anticipate a kind of or combination of at least two.
9. according to the method for coating described in any one of claim 1-8, it is characterised in that said method comprising the steps of:
(1) make the mixed liquor reaction 0.5-72h comprising electrode material, slaine and chelating agent, carry out after having reacted filtering, clearly
Wash and dry in 50～200 DEG C, obtain the electrode material of metallic organic framework cladding；
(2) electrode material being coated with by metallic organic framework is in 200～900 DEG C of heat treatment 0.5～10h in atmosphere,
To oxide jacketed electrode material.
10. the method for coating as described in any one of claim 1-9 prepares oxide jacketed electrode material, and its feature exists
In, described oxide jacketed electrode material comprises electrode material and is coated on the metal-oxide cladding of electrode material surface
Layer；
Preferably, the chemical analysis of described metal-oxide clad includes aluminium oxide, magnesium oxide, titanium oxide, zinc oxide, oxidation
Any one or the combination of at least two in cobalt, vanadium oxide, chromium oxide, ferrum oxide, zirconium oxide or nickel oxide；
Preferably, described metal-oxide clad is 0～20% with the mass ratio of electrode material, and does not include 0%, is preferably
0.25～10%.
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