CN1979929A - Lamina-structure lithium-contained composite metal oxide coated with carbon and use thereof - Google Patents
Lamina-structure lithium-contained composite metal oxide coated with carbon and use thereof Download PDFInfo
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- CN1979929A CN1979929A CNA2005101264296A CN200510126429A CN1979929A CN 1979929 A CN1979929 A CN 1979929A CN A2005101264296 A CNA2005101264296 A CN A2005101264296A CN 200510126429 A CN200510126429 A CN 200510126429A CN 1979929 A CN1979929 A CN 1979929A
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Abstract
Being as composite material with a nucleocapsid structure, the disclosed core material is in laminated structure of composite metal oxide granules containing lithium, and carbon layer as shell covers granule. Structural features of the composite metal oxide material are that oxygen atom layer, lithium atom layer, oxygen atom layer, metal layer and oxygen atom layer are arranged alternately in sequence in direction perpendicular to c axis in crystal structure. The composite metal improves surface electron conductance and electric contact so as to raise charging and discharging specific capacity and magnification performance. Features are: high charging and discharging efficiency, improved cycle performances, low cost and no pollution, high energy density of lithium cell of using the composite material as material for positive pole, safety, and applicable to multiform occasion.
Description
Technical field
The invention belongs to the material technology field, specifically relate to a kind of lamina-structure lithium-contained composite metal oxide of coated with carbon, and in the application of making in the high-energy density secondary lithium battery positive pole material.
Background technology
The positive electrode active materials of serondary lithium battery mainly contains the LiCoO of layer structure at present
2, LiNiO
2And LiNi
xCo
2-xMn
xO
2And the LiMn of spinel structure
2O
4LiFePO with olivine structural
4Deng.The LiMn of spinel structure wherein
2O
4Capacity is 110mAh/g, is suitable for high-power battery, the LiFePO of olivine structural
4Capacity is 150mAh/g, and its density is lower, and high rate performance is relatively poor, but fail safe is better.This two classes material all is not suitable for being applied in high-energy density secondary lithium battery.
Mainly use compound at present in the high-energy density secondary lithium battery with layer structure.LiCoO wherein
2Actual specific capacity is the positive electrode active materials that is applied to the commodity serondary lithium battery the earliest between 130-145mAh/g, and its stable performance is easy to synthesize, and has obtained being extensive use of.But, because the Co price is more expensive, therefore with LiCoO
2For the serondary lithium battery of positive electrode is difficult to reduce cost, and the lithium storage content of this material can not satisfy the requirement of existing market to high-energy density secondary lithium battery positive pole material.With respect to LiCoO
2, layer structure LiNiO
2Production cost to hang down, but synthetic single-phase LiNiO
2Very big difficulty is arranged on technology, and LiNiO
2Structure also not as LiCoO
2Stable, capacity is decayed fast in charge and discharge process.On this basis, invention at present have a binary LiNi
xM
yO
2, LiCo
xM
yO
2, LiMn
xM
yO
2Or ternary material LiNi
xCo
2-xMn
xO
2, all having higher relatively capacity, 140-180mAh/g has obtained certain applications.But, the requirement of energy content of battery density is improved constantly along with the upgrading of growing consumption electronic product.Having more, high power capacity, serondary lithium battery cheap, that cyclicity is good are still present development priority.And develop new positive electrode is one of key technology wherein.
Its capacity of the positive electrode of serondary lithium battery is relevant with reactive metal element variable valency scope in the positive electrode.The aforementioned lamellar compound of mentioning embeds in the process at lithium ion, mainly is that Ni, Co, three kinds of element generations of Mn electron transfer are redox reaction, because the chemical valence variable valency scope of these three kinds of elements is monovalence and divalence, so its capacity is lower.
Known element with higher variable valency is Cr, V, and Nb, Mo and W, and have LiCrO with layer structure
2, LiVO
2, LiNbO
2, LiMoO
2Deng compound, but these compound electro-chemical activities are lower, and lithium ion can not be deviate from.Discover (document 1:Y.Grincourt, C.Storey, and I.J.Davidson, J.Power Sources, 97-98,711 (2001)), have expression formula Li[Cr for nearest one
xLi
(1/3-2x/3)Mn
(2/3-2x/3)] O
2Lamellar compound have the higher lithium capacity that takes off, and higher reversible capacity, 180-210mAh/g has shown certain advantage with it as positive electrode, but this material cyclicity is relatively poor, this with this material in all metallic elements to be variable valency element (for example Cr, Mn) relevant.And the high rate performance of this material is relatively poor, can not heavy-current discharge, and this is low relevant with this material electronics conductivity and ionic conductivity.
Above-mentioned all have the positive electrode of layer structure, all synthetic in air or oxygen.Since contain Co, Ni, and these elements of Mn are being attempted when its particle surface coats carbon-coating, Co, Ni, reduction has taken place in Mn, formed the compound of lower valency and directly restored metal, original layer structure no longer keeps, and can not be re-used as the positive electrode of lithium ion battery.Therefore up to now, the report of the lamellar compound of coated with carbon material is not arranged as yet.Nearest studies show that (document 1:J.-M.TarasconM.Armand, Nature, 414,359 (2001)) are for the LiFePO with olivine structural
4Can carry out carbon and coat under inert atmosphere and reducing atmosphere, the surface conductance that coats the back particle improves greatly, thereby has obtained the material of high rate performance excellence.LiFePO
4Be the low-down insulator of electronic conductivity, this shows that the carbon coating has significant effect for surface conductance that improves material and high rate performance.
Summary of the invention
The objective of the invention is to overcome above-mentioned defective, provide a kind of can be so that serondary lithium battery has the positive electrode of high power capacity more, cheap, advantage that cyclicity is good.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of lamina-structure lithium-contained composite metal oxide of coated with carbon, it is the composite material of a nucleocapsid structure, and core material is the lithium-contained composite metal oxide particle with layer structure, is " shell " that a coating carbon-coating forms on its surface.
The architectural feature of the lithium-contained composite metal oxide of described layer structure as core material is: on perpendicular to the c direction of principal axis in the crystal structure, and alternately arranging successively oxygen atomic layer, lithium atom layer, oxygen atomic layer, metal level and oxygen atomic layer; Wherein, in the metal level for being selected from active element Cr, V, Nb, Mo, one or more in W and the nonactive element M, and the total chemical valence of each element of metal level is 3, satisfies electroneutral requirement.
The element of described nonactive element M for appraising at the current rate in charge and discharge process comprises that chemical valence is the Li and the Na of monovalence, and chemical valence is the Mg of divalence, and Ca, Sr and Zn, chemical valence are the Al of trivalent, Ga, and Sc, Y, La chemical valence are the Ti of tetravalence, Zr, Si, Ge.
Because the needs of charge balance when nonactive element M is divalence, must exist above-mentioned quadrivalent element to keep charge balance; When M is tetravalence, both can select above-mentioned diad coexistence, also can in metal level, introduce univalent element and keep charge balance.No matter contain the metal of tetravalence, trivalent, divalence or monovalence in the metal level, total chemical valence should be 3, satisfy electroneutral requirement.This material allows above-mentioned multiple element to coexist as in the metal level of this layer structure.
The general formula that the lithium-contained composite metal oxide of above-mentioned layer structure one of meets in the chemical formula of following (1)～(4):
(1)Li[M
0 xM
1 (1/2-x/2)M
2 (1/2-x/2)]O
2-yX
z
Wherein, M
0For being selected from Cr, V, Nb, Mo, one or more among the W;
M
1For being selected from Mg, Ca, Sr, one or more among the Zn;
M
2For being selected from Ti, Zr, Si, one or more among the Ge;
X is for being selected from F, S, one or more among the N;
0.2≤x≤0.9，0≤y≤0.1，0≤z≤0.2；
(2)Li[M
0 xM
1 (1/3-1x/3)M
2 (2/3-2x/3)]O
2-yX
z
Wherein, M
0For being selected from Cr, V, Nb, Mo, one or more among the W;
M
1For Li or/and Na;
M
2For being selected from Ti, Zr, Si, one or more among the Ge;
X is for being selected from F, S, one or more among the N;
0.2≤x≤0.9，0≤y≤0.1，0≤z≤0.2；
(3)LiM
0 xM
1-xO
2-yX
z
Wherein, M
0For being selected from Cr, V, Nb, Mo, one or more among the W;
M is for being selected from Al, Ga, Sc, Y, La, one or more among the In;
X is for being selected from F, S, one or more among the N;
0.2≤x≤0.9，0≤y≤0.1，0≤z≤0.2；
(4)Li[M
0 xM
1 (1/2-x/2-w/2)M
2 wM
3 (1/2-x/2-w/2)]O
2-yX
z
M wherein
0For being selected from Cr, V, Nb, Mo, one or more among the W;
M
1For being selected from Mg, Ca, Sr, one or more among the Zn;
M
2For being selected from Al, Ga, Sc, Y, La, one or more among the In;
M
3For being selected from Ti, Zr, Si, one or more among the Ge;
X is for being selected from F, S, one or more among the N;
0.2≤x≤0.9，0＜w＜0.8，0≤y≤0.1，0?≤?z≤0.2。
" shell " that described coating carbon-coating forms, form by the carbon of disordered structure, thickness is the carbon-coating of 2nm～5 μ m; The percentage by weight that this carbon-coating material accounts for whole composite material is 0.1～10wt%.
" shell " that described coating carbon-coating forms, form by the hard carbon of conductive carbon particle and continuous disordered structure, thickness is the compound carbon-coating of 10 nm～10 μ m; The percentage by weight that this compound carbon-coating accounts for whole composite material is 0.1～20wt%.Wherein, described conductive carbon particle is a carbon black, acetylene black, and spherical graphite, diameter are 2nm～2 μ m.
" shell " that described coating carbon-coating forms is that one that be made up of carbon nano-tube or carbon nano-fiber, thickness (being carbon nano-tube or carbon nano-fiber length) is the carbon-coating of 50nm～10 μ m; The percentage by weight that this carbon-coating material accounts for whole composite material is 0.1～10wt%.Wherein, the diameter of described carbon nano-tube or nanofiber is 2～500nm, and the caliber of carbon nano-tube is 1～20nm; Described carbon nano-tube or nanofiber both can be straight, also can be crooked.
The lamina-structure lithium-contained composite metal oxide of coated with carbon provided by the invention is to synthesize its core---the lithium-contained composite metal oxide of layer structure earlier under inert atmosphere, coat one deck carbon at its particle surface by pyrolysis or chemical gaseous phase depositing process then, form the carbon clad composite material.
When preparing the lithium-contained composite metal oxide of layer structure, sol-gal process can be adopted, also solid phase method can be adopted.Adopt the process of Prepared by Sol Gel Method to be summarized as follows: will contain Li, M
0And M
1, M
2, M
3Presoma dissolving, add precipitation reagent and form collosol and gel, the heating solvent evaporated obtains presoma, presoma is ground, earlier at 250～600 ℃ of (air, nitrogen or argon gas) in sintering 2～48 hours, after grinding once more, sintering 2～48 hours in 500～1000 ℃ of inert gases (nitrogen or argon gas) again.Solid phase method is first with Li, M
0And M
1, M
2, M
3Presoma mix, sintering in 250～600 ℃ of air then, after grinding once more, sintering 2～48 hours in 500～1000 ℃ of inert gases (nitrogen or argon gas) again.
When outside the lithium-contained composite metal oxide of layer structure, coating carbon-coating, different according to the composition of coated with carbon bed with structure, can adopt following several different methods preparation.
(1) the direct chemical vapour deposition process is used for single carbon-coating coating.The core material lamina-structure lithium-contained composite metal oxide is positioned over is connected with inert gas (nitrogen, argon gas) with the tube furnace of carbon-source gas (ethene, acetylene, methane or toluene etc.) in, 500～1000 ℃ of heating 2～48 hours, then at this core material particle surface deposition one deck carbon.
(2) pyrolysismethod is used for single carbon-coating coating.With core material with contain the aqueous solution of carbon source (as sucrose, starch, yellow starch gum, pitch, epoxy resin, polyvinyl alcohol, Kynoar) or organic solvent and mix after, evaporate to dryness water or organic solvent, be connected with inert gas (nitrogen, argon gas) in the tube furnace, 500～1000 ℃ of heating 2～48 hours, then at this core material particle surface deposition one deck carbon.
(3) two step chemical vapour deposition techniques are used for compound carbon-coating and coat.With the ultra-fine carbon granule of core material lamina-structure lithium-contained composite metal oxide and conduction (as carbon black, superfine graphite, acetylene black, carbon fiber, carbon nano-tube), the presoma of carbon is (as sucrose, starch, phenolic resins, pitch, poly(ethylene oxide), Kynoar etc.) in advance by after the mechanical agitation mixing, in being connected with the tube furnace of inert gas, 300～1000 ℃ of heating 2～48 hours, drop to room temperature then, take out back mechanical lapping, sieve, after the classification, place tube furnace once more, feed inert gas and carbon-source gas, heated 2～48 hours, then at this core material particle surface, form the compound carbon-coating of parcel ultrafine electricity conductive particle, the method is called two step chemical vapour deposition techniques.
(4) chemical vapour deposition (CVD) is used for the carbon nano-tube coating.Adopt general infusion process with Fe, catalyst granuless such as Ni are dispersed in core material lamina-structure lithium-contained composite metal oxide particle surface, with area load the core material particle of catalyst place tube furnace, feed inert gas (nitrogen, argon gas) with carbon-source gas (ethene, acetylene, methane or toluene etc.), 500～1000 ℃ of heating 0.5～48 hour, then, form the cage structure that the superficial growth carbon nano-tube is wrapped up inner lamina-structure lithium-contained composite metal oxide particle in this core material particle surface deposition one deck carbon nano-tube.
By above four kinds of methods, can prepare the carbon coating layer shape structure lithium-contained composite metal oxide composite material that the surface has the different structure carbon coating layer.
In the process that coats, within certain temperature range, the core of composite material of the present invention can keep Stability Analysis of Structures, can not undergo phase transition.Coat by carbon, the surface electronic electricity of composite material is led and is electrically contacted improvement greatly, has also prevented the redox side reaction of high valence elements and electrolyte simultaneously.
The lamina-structure lithium-contained composite metal oxide of coated with carbon provided by the invention is based on the carbon coating layer shape structure lithium-contained composite metal oxide composite material of six side's layered crystal structures, its core material adopts the lithium-contained composite metal oxide with layer structure of special composition, and active element is high variable valency element.In addition because the surface electronic electricity is led and the improvement greatly that electrically contacts, and charging and discharging capacity and high rate performance further improve, efficiency for charge-discharge and cycle performance also be improved significantly, and material price is cheap, preparation technology is simple.
The lamina-structure lithium-contained composite metal oxide of coated with carbon provided by the invention can be used in the serondary lithium battery as positive electrode active materials.
With the similar of composite material of the present invention as the basic structure of the serondary lithium battery of positive electrode and present serondary lithium battery, comprise material of the present invention is the positive pole of positive electrode active materials, general negative pole, general organic or inorganic electrolyte solution or polymer dielectric or solid electrolyte are electrolyte, general barrier film, collector, battery case and lead-in wire are formed.Positive pole is burn-on respectively with an end of negative pole, and lead-in wire is back to link to each other with the battery case two ends or the electrode column of mutually insulated.With the serondary lithium battery of material of the present invention as positive electrode active materials, can make button (individual layer), cylindrical (multilaminate coiled) by above-mentioned basic structure, square various ways and specifications such as (multilayer foldings), and be not limited thereto.The usefulness that obtains thus composite material of the present invention is as the serondary lithium battery energy density height of positive electrode, and cyclicity is good, and is safe and reliable, and particularly good rate capability can be applied to multiple occasion.
Embodiment
Embodiment 1
With 0.02mol Cr (NO
3)
39H
2O, 0.1267mol CH
3COOLi2H
2O and 0.0533mol Si (OC
2H
5)
4Be dissolved in The addition of C H
3CH
2Among the OH, slowly add NH
3H
2O, the pH value of regulator solution is 9.5～10.5, leaves standstill the formation gel, places it in 10 hours solvent evaporated in 100 ℃ of baking ovens, obtains presoma.With the presoma mechanical ball milling after 4 hours, under 400 ℃ of Ar gas, heating is 10 hours in the tube furnace, mechanical ball milling 4 hours again after the cooling, and insulation obtained Li[Cr in 10 hours in 900 ℃ of Ar gas pipe type stoves again
0.2Li
0.267Si
0.533] O
2With Li[Cr
0.2Li
0.267Si
0.533] O
2Place tube furnace once more, feed toluene gas at 600 ℃ and drop to room temperature after 30 minutes, obtain the lamina-structure lithium-contained composite metal oxide composite material 1 that the surface coats unordered carbon-coating, this material is through chemical analysis, and its carbon content is about 0.1%.This material is studied through transmission electron microscope, and its carbon-coating thickness is 2nm.
The composite material 1 that obtains is mixed formation slurry (active material: acetylene black: PVDF=90: 5: 5) at normal temperatures and pressures with the n-formyl sarcolysine base pyrrolidone solution of acetylene black and 10% Kynoar (PVDF), evenly be coated on the aluminum substrates, then 100 ℃ of vacuumizes after 5 hours, the film of gained is compressed under 10MPa pressure, the about 100 μ m of the film thickness of gained are cut into the positive pole of the electrode slice of 1 * 1cm as simulated battery.
The negative pole of simulated battery uses the lithium sheet, and electrolyte is 1mol LiPF
6Be dissolved in the mixed solvent of 1L EC and DMC (volume ratio 1: 1).With positive pole, negative pole, electrolyte, barrier film is assembled into simulated battery in the glove box of argon shield.
The electro-chemical test step of simulated battery: at first charge to 4.3V with 30mA/g, be discharged to 2.0V with same current density then, the capacity of being emitted reaches 120mAh/g with the Mass Calculation of composite material, the initial charge/discharge efficient of this material is 80%, circulate after 50 times, reversible capacity remains on 115mAh/g.When discharging current increased to 100mA/g, the discharge capacity of this material was 80mAh/g, and this current density is equivalent to the charge-discharge magnification of 1C, and when further raising current density during to 1000mA/g, the discharge capacity of this material is 60mAh/g.This result shows that composite material 1 has high-multiplying power discharge characteristic preferably.
Embodiment 2
With 0.01mol Cr
2O
3, 0.06335mol Li
2CO
3With 0.0533mol SiO
2The mixing machinery ball milling obtained presoma in 4 hours, and insulation obtained Li[Cr in 10 hours under 900 ℃ of Ar gas then
0.2Li
0.267Si
0.533] O
2With embodiment 1, at Li[Cr
0.2Li
0.267Si
0.533] O
2Coated with carbon bed, different is, and carbon source gas is acetylene, and reaction temperature is 800 ℃, and temperature retention time is 8 hours, the carbon that obtains having nucleocapsid structure coats Li[Cr
0.2Li
0.267Si
0.533] O
2Composite material 2.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 3
Be similar to embodiment 1, change the metering ratio of presoma, adopt sol-gal process to obtain Li[Cr
0.2Li
0.4Si
0.2] O
2With embodiment 1, at Li[Cr
0.2Li
0.267Si
0.533] O
2Coated with carbon bed, different is, and carbon source gas is ethene, and reaction temperature is 1000 ℃, and temperature retention time is 24 hours, the carbon that obtains having nucleocapsid structure coats Li[Cr
0.4Li
0.2Si
0.4] O
2Composite material 3 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 4
Be similar to embodiment 1, change the metering ratio of presoma, adopt sol-gal process to obtain Li[Cr
0.9Li
0.033Si
0.067] O
2With embodiment 1, at Li[Cr
0.2Li
0.267Si
0.533] O
2Coated with carbon bed, different is, and carbon source gas is methane, and reaction temperature is 1000 ℃, and temperature retention time is 48 hours, cooling obtains carbon and coats Li[Cr
0.9Li
0.033Si
0.067] O
2Composite material 4 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 5
Be similar to embodiment 2, adopt solid reaction process to obtain, different is to adopt 0.01molV
2O
3With GeO
2As presoma.With 50 gram Li[V
0.2Li
0.267Ge
0.533] O
2Powder is dispersed to and contains water soluble starch 8 gram, and 80ml distilled water in the container of 20 milliliters of ethanol, heats this beaker while stirring, makes water evaporate to dryness in 2 hours.Products therefrom is incubated 5 hours in 600 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[V
0.2Li
0.267Ge
0.533] O
2Composite material 5 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 6
Be similar to embodiment 5, adopt solid reaction process to obtain Li[Cr
0.4Na
0.2Ge
0.4] O
2, different is that presoma changes the Cr with 0.02mol into
2O
3, 0.05mol Li
2CO
3, 0.01mol Na
2CO
3With 0.04mol GeO
2Mix, all the other steps are identical.With 50 gram Li[Cr
0.4Na
0.2Ge
0.4] O
2Powder is dispersed to and contains yellow starch gum 12 gram, and 80ml distilled water in the container of 20 milliliters of ethanol, heats this beaker while stirring, makes water evaporate to dryness in 2 hours.Products therefrom is incubated 8 hours in 800 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[Cr
0.4Na
0.2Ge
0.4] O
2Composite material 6 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 7
Be similar to embodiment 5, adopt solid reaction process to obtain Li[V
0.9Na
0.033Ge
0.067] O
2With 50 gram Li[V
0.9Na
0.033Ge
0.067] O
2Powder is dispersed to and contains sucrose 16 gram, and 80ml distilled water in the container of 20 milliliters of ethanol, heats this beaker while stirring, makes water evaporate to dryness in 2 hours.Products therefrom is incubated 8 hours in 900 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[V
0.9Na
0.033Ge
0.067] O
2Composite material 7 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 8
Be similar to embodiment 2, adopt solid reaction process to obtain Li[Cr
0.2Na
0.267Zr
0.533] O
2, different is to adopt ZrO
2As presoma.With 50 gram Li[Cr
0.2Na
0.267Zr
0.533] O
2Powder is dispersed to and contains yellow starch gum 16 gram, and 80ml distilled water in the container of 20 milliliters of ethanol, heats this beaker while stirring, makes water evaporate to dryness in 2 hours.Products therefrom is incubated 8 hours in 600 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[Cr
0.2Na
0.267Zr
0.533] O
2Composite material 7 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 9
Be similar to embodiment 8, adopt solid reaction process to obtain Li[Cr
0.4Na
0.2Zr
0.4] O
2With 50 gram Li[Cr
0.4Na
0.2Zr
0.4] O
2Powder is dispersed to and contains yellow starch gum 12 gram, and 80ml distilled water in the container of 20 milliliters of ethanol, heats this beaker while stirring, makes water evaporate to dryness in 2 hours.Products therefrom is incubated 8 hours in 500 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[Cr
0.4Na
0.2Zr
0.4] O
2Composite material 7 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 10
Be similar to embodiment 8, adopt solid reaction process to obtain Li[Cr
0.9Na
0.033Zr
0.067] O
2With 50 gram Li[Cr
0.9Na
0.033Zr
0.067] O
2Powder is dispersed to and contains yellow starch gum 12 gram, and 80ml distilled water in the container of 20 milliliters of ethanol, heats this beaker while stirring, makes water evaporate to dryness in 2 hours.Products therefrom is incubated 8 hours in 600 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[Cr
0.9Na
0.033Zr
0.067] O
2Composite material 10 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 11
Be similar to embodiment 1, with 0.04mol Cr (NO
3)
39H
2O, 0.12mol CH
3COOLi2H
2O and 0.04molTi (OC
4H
9)
4Be reactant, prepare Li[Cr according to embodiment 1 identical condition
0.4Li
0.2Ti
0.4] O
2With 50 gram Li[Cr
0.4Li
0.2Ti
0.4] O
2Powder is dispersed to and contains yellow starch gum 16 gram, and 80ml distilled water in the container of 20 milliliters of ethanol, heats this beaker while stirring, makes water evaporate to dryness in 2 hours.With products therefrom at 1000 ℃ of ethene: insulation is after 48 hours in argon gas (1: 1) the pipe type stove, and cooling obtains carbon and coats Li[Cr
0.4Li
0.2Ti
0.4] O
2Composite material 11 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 12
Be similar to embodiment 11, obtain Li[Cr
0.3Li
0.233Ti
0.467] O
2With 50 gram Li[Cr
0.3Li
0.233Ti
0.467] O
2Powder is dispersed to bituminous 8 grams, in the container of 80ml carbon tetrachloride, heats this beaker while stirring, makes carbon tetrachloride evaporate to dryness in 1 hour.Products therefrom is incubated 8 hours in 600 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[Cr
0.3Li
0.233Ti
0.467] O
2Composite material 12 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 13
Be similar to embodiment 2, with 0.02mol Nb
2O
3, 0.12mol LiOH2H
2O, 0.02mol ZrO
2And 0.02molTiO
2Be reactant, prepare Li[Nb according to embodiment 2 identical conditions
0.4Li
0.2Ti
0.2Zr
0.2] O
2With 50 gram Li[Nb
0.4Li
0.2Ti
0.2Zr
0.2] O
2Powder is dispersed to and contains epoxy resin 8 gram, in the 100ml acetone container, heats this beaker while stirring, makes acetone evaporate to dryness in 1 hour.Products therefrom is incubated 8 hours in 600 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[Nb
0.4Li
0.2Ti
0.2Zr
0.2] O
2Composite material 13 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 14
Be similar to embodiment 1, with 0.04mol Cr (NO
3)
39H
2O, 0.12mol CH
3COOLi2H
2O, 0.03molTi (OC
4H
9)
4And 0.01molSi (OC
2H
5)
4Be reactant, prepare Li[Cr according to embodiment 1 identical condition
0.4Li
0.2Ti
0.3Si
0.1] O
2With 50 gram Li[Cr
0.4Li
0.2Ti
0.3Si
0.1] O
2Powder is dispersed to and contains polyvinyl alcohol 8 gram, in the 100ml distilled water, heats this beaker while stirring, makes water evaporate to dryness in 2 hours.Products therefrom is incubated 48 hours in 600 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[Cr
0.4Li
0.2Ti
0.3Si
0.1] O
2Composite material 14 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 15
Be similar to embodiment 2, with 0.02mol Cr
2O
3, 0.12mol LiOH2H
2O, 0.02mol TiO
2, 0.01molZrO
2And 0.01molGeO
2Be reactant, prepare Li[Cr according to embodiment 2 identical conditions
0.4Li
0.2Ti
0.2Zr
0.1Ge
0.1] O
2With 50 gram Li[Cr
0.4Li
0.2Ti
0.2Zr
0.1Ge
0.1] O
2Powder is dispersed to and contains Kynoar 8 gram, in the container of 100ml n-formyl sarcolysine base pyrrolidones, heats this beaker while stirring, makes n-formyl sarcolysine base pyrrolidones evaporate to dryness in 2 hours.Products therefrom is incubated 8 hours in 600 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[Cr
0.4Li
0.2Ti
0.2Zr
0.1Ge
0.1] O
2Composite material 15 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 16
Be similar to embodiment 2, with 0.02mol Cr
2O
3, 0.12mol LiOH2H
2O, 0.01mol TiO
2, 0.01molZrO
2, 0.01mol SiO
2With 0.01mol GeO
2Be reactant, prepare Li[Cr according to embodiment 2 identical conditions
0.4Li
0.2Ti
0.1Zr
0.1Ge
0.1Si
0.1] O
2With 50 gram Li[Cr
0.4Li
0.2Ti
0.1Zr
0.1Ge
0.1Si
0.1] O
2Powder is dispersed to and contains yellow starch gum 8 gram, and 80ml distilled water in the container of 20 milliliters of ethanol, heats this beaker while stirring, makes water evaporate to dryness in 2 hours.Products therefrom is incubated 2 hours in 500 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[Cr
0.4Li
0.2Ti
0.1Zr
0.1Ge
0.1Si
0.1] O
2Composite material 16 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 17
Be similar to embodiment 2, with 0.02mol Cr
2O
3, 0.11mol LiOH2H
2O, 0.04mol ZrO
2With 0.01molLiF be reactant, prepare Li[Cr according to embodiment 2 identical conditions
0.4Li
0.2Zr
0.4] O
1.9F
0.1With 50 gram Li[Cr
0.4Li
0.2Zr
0.4] O
1.9F
0.1Powder is dispersed to and contains yellow starch gum 8 gram, and 80ml distilled water in the container of 20 milliliters of ethanol, heats this beaker while stirring, makes water evaporate to dryness in 2 hours.Products therefrom is incubated 4 hours in 1000 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[Cr
0.4Li
0.2Zr
0.4] O
1.9F
0.1Composite material 17 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 18
Be similar to embodiment 2, with 0.02mol Mo
2O
3, 0.10mol LiOH2H
2O, 0.04mol ZrO
2With 0.02molLiF be reactant, prepare Li[Mo according to embodiment 2 identical conditions
0.4Li
0.2Zr
0.4] O
1.9F
0.2With 50 gram Li[Mo
0.4Li
0.2Zr
0.4] O
1.9F
0.2Powder is dispersed to and contains yellow starch gum 8 gram, and 80ml distilled water in the container of 20 milliliters of ethanol, heats this beaker while stirring, makes water evaporate to dryness in 2 hours.Products therefrom is incubated 48 hours in 500 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[Mo
0.4Li
0.2Zr
0.4] O
1.9F
0.2Composite material 18 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 19
Be similar to embodiment 2, with 0.02mol Cr
2O
3, 0.10mol LiOH2H
2O, 0.04mol ZrO
2And 0.01molLi
2S is a reactant, prepares Li[Cr according to embodiment 2 identical conditions
0.4Li
0.2Zr
0.4] O
1.9S
0.1With 50 gram Li[Cr
0.4Li
0.2Zr
0.4] O
1.9S
0.1Powder is dispersed to and contains yellow starch gum 8 gram, and 80ml distilled water in the container of 20 milliliters of ethanol, heats this beaker while stirring, makes water evaporate to dryness in 2 hours.Products therefrom is incubated 24 hours in 600 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[Cr
0.4Li
0.2Zr
0.4] O
1.9S
0.1Composite material 19 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 20
Be similar to embodiment 2, with 0.02mol V
2O
3, 0.09mol LiOH2H
2O, 0.04mol ZrO
2And 0.01molLi
3N is a reactant, and (sintering atmosphere is N according to embodiment 2 identical conditions
2) prepare Li[V
0.4Li
0.2Zr
0.4] O
1.9N
0.1With 50 gram Li[V
0.4Li
0.2Zr
0.4] O
1.9N
0.1Powder is dispersed to and contains yellow starch gum 8 gram, and 80ml distilled water in the container of 20 milliliters of ethanol, heats this beaker while stirring, makes water evaporate to dryness in 2 hours.Products therefrom is incubated 48 hours in 600 ℃ of Ar gas pipe type stoves after, cooling obtains carbon and coats Li[V
0.4Li
0.2Zr
0.4] O
1.9N
0.1Composite material 20 adopts to prepare electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 21
Be similar to embodiment 1, with 0.02mol Cr (NO
3)
39H
2O, 0.1mol CH
3COOLi2H
2O and 0.08molAl (NO
3)
3Be dissolved in the suitable quantity of water, slowly add NH
3H
2O, the pH value of regulator solution is 7.0-8.0, leaves standstill the formation gel, places it in 10 hours solvent evaporated in 100 ℃ of baking ovens, obtains presoma.With presoma mechanical ball milling 4 hours, heating was 10 hours under 400 ℃ of Ar gas, mechanical ball milling 4 hours again after the cooling, and insulation obtained LiCr in 10 hours under 900 ℃ of Ar gas again
0.2Al
0.8O
2With 50 gram LiCr
0.2Al
0.8O
2Powder, with 2 gram conductive carbon blacks (particle diameter is 2nm), 10 gram sucrose mix, adopt the method for mechanical ball milling, ball milling is after 4 hours, under 1000 ℃ of Ar gas, heating is 2 hours in the tube furnace, mechanical ball milling is after 4 hours again after the cooling, and 600 mesh sieves are placed on the powder after sieving in the tube furnace once more excessively, under Ar gas, be warming up to 1000 ℃, (acetylene: argon gas=1: 1), be incubated after 2 hours, cooling obtains the LiCr that the surface coats compound carbon-coating to switch carbon source gas then
0.2Al
0.8O
2Composite material 21.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 22
Be similar to embodiment 1, adopt sol-gal process to obtain LiCr
0.5Al
0.5O
2With 50 gram LiCr
0.5Al
0.5O
2Powder, with 5 gram acetylene blacks (average grain diameter is 5nm), 20 gram sucrose mix, adopt the method for mechanical ball milling, ball milling is after 4 hours, under 800 ℃ of Ar gas, heating is 10 hours in the tube furnace, mechanical ball milling is after 4 hours again after the cooling, and 600 mesh sieves are placed on the powder after sieving in the tube furnace once more excessively, under Ar gas, be warming up to 800 ℃, (acetylene: argon gas=1: 1), be incubated after 48 hours, cooling obtains the LiCr that the surface coats compound carbon-coating to switch carbon source gas then
0.5Al
0.5O
2Composite material 22.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 23
Be similar to embodiment 1, adopt sol-gal process to obtain LiCr
0.9Al
0.1O
2With 50 gram LiCr
0.9Al
0.1O
2Powder, with 1 gram conductive carbon black (average grain diameter is 2nm), 5 gram yellow starch gums mix, adopt the method for mechanical ball milling, ball milling is after 4 hours, under 300 ℃ of Ar gas, heating is 48 hours in the tube furnace, mechanical ball milling is after 4 hours again after the cooling, and 600 mesh sieves are placed on the powder after sieving in the tube furnace once more excessively, under Ar gas, be warming up to 700 ℃, switch to ethylene gas then, be incubated after 24 hours, cooling obtains the LiCr that the surface coats compound carbon-coating
0.9Al
0.1O
2Composite material 23.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 24
Be similar to embodiment 1, with 0.05mol Cr (NO
3)
39H
2O, 0.1mol CH
3COOLi2H
2O and 0.05molSc (NO
3)
3Be reactant, prepare LiCr according to embodiment 1 identical condition
0.5Sc
0.5O
2With 50 gram LiCr
0.5Sc
0.5O
2Powder, with 1 gram superfine graphite (average grain diameter is 2 μ m), 5 gram starch mix, adopt the method for mechanical ball milling, ball milling is after 4 hours, under 600 ℃ of Ar gas, heating is 10 hours in the tube furnace, mechanical ball milling is after 4 hours again after the cooling, and 600 mesh sieves are placed on the powder after sieving in the tube furnace once more excessively, under Ar gas, be warming up to 700 ℃, (ethane: argon gas=1: 1), be incubated after 10 hours, cooling obtains the LiCr that the surface coats compound carbon-coating to switch carbon source gas then
0.5Sc
0.5O
2Composite material 24.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 25
Be similar to embodiment 1, with 0.05mol Cr (NO
3)
39H
2O, 0.1mol CH
3COOLi2H
2O and 0.05molY (NO
3)
3Be reactant, prepare LiCr according to embodiment 1 identical condition
0.5Y
0.5O
2Take by weighing 0.01molNi (NO
3)
26H
2O puts into beaker, adds 100ml ethylene glycol, stirring and dissolving.With 2gLiCr
0.5Y
0.5O
2Powder joins 0.1MNi (NO
3)
26H
2In the O100ml ethylene glycol solution, stirred 10 hours at 60 ℃, by Buchner funnel or other filter plant with Separation of Solid and Liquid, then 80 ℃ of following vacuumizes 10 hours.With LiCr
0.5Y
0.5O
2Powder load the material of Ni catalyst be placed in the aluminium oxide boat, the tube furnace of packing into then charges into argon gas, and flow is 80sccm, after the temperature programming to 700 ℃, gas is converted to the gaseous mixture of acetylene and argon gas, and its ratio is 3: 2 (v/v), and total flow is 100sccm, after constant temperature carried out chemical vapour deposition (CVD) in 0.5 hour, gas is converted to argon gas, naturally cools to room temperature, the LiCr of products therefrom superficial growth carbon nano-tube
0.5Y
0.5O composite material 25, wherein the average diameter of carbon nano-tube is 2nm, and length is 50nm, and caliber is 1nm.Other parameter and electrochemical property test the results are shown in table 1.
Embodiment 26
Be similar to embodiment 1, with 0.09mol Cr (NO
3)
39H
2O, 0.1mol CH
3COOLi2H
2O and 0.01molLa (NO
3)
3Be reactant, prepare LiCr according to embodiment 1 identical condition
0.9La
0.1O
2Be similar to embodiment 25, prepare the LiCr of superficial growth carbon nano-tube
0.9La
0.1O
2Composite material 26, different is constant temperature 48 hours.The average diameter of carbon nano-tube is 100nm, and length is 10 μ m, and caliber is 2nm.Other parameter and electrochemical property test the results are shown in table 1.
Embodiment 27
Be similar to embodiment 2, with 0.025mol Cr
2O
3, 0.1mol LiOH2H
2O and 0.025mol Ga
2O
3Be reactant, prepare LiCr
0.5Ga
0.5O
2Be similar to embodiment 25, prepare the LiCr of superficial growth carbon nano-tube
0.5Ga
0.5O
2Composite material 27, different is to adopt 0.2M Ni (NO
3)
26H
2As catalyst precursor, all the other conditions are with embodiment 26 in the O 100ml ethanolic solution.The average diameter of carbon nano-tube is 500nm, and length is 10 μ m, and caliber is 20nm.Other parameter and electrochemical property test the results are shown in table 1.
Embodiment 28
Be similar to embodiment 1, with 0.05mol Cr (NO
3)
39H
2O, 0.1mol CH
3COOLi2H
2O and 0.05molIn (NO
3)
33H
2O is a reactant, prepares LiCr according to embodiment 1 identical condition
0.5In
0.5O
2Take by weighing 0.0001mol (NH
4)
6Mo
7O
244H
2O puts into beaker, adds 100ml methyl alcohol, stirring and dissolving; Then with 10gLiCr
0.5Ga
0.5O
2Powder joins in this solution, stirred 10 hours at 25 ℃, by Buchner funnel or other filter plant with Separation of Solid and Liquid, then 100 ℃ of following vacuumizes 10 hours; The gained material is placed in the aluminium oxide boat, the tube furnace of packing into then, charge into argon gas, flow is 80sccm, after the temperature programming to 800 ℃, gas is converted to argon gas stream crosses the toluene bottle, flow is 100sccm, and constant temperature was converted to argon gas with gas after carrying out chemical vapour deposition (CVD) in 48 hours, naturally cool to room temperature, products therefrom is the LiCr of superficial growth carbon fiber
0.5Ga
0.5O
2Composite material, average diameter of carbon fiber is 500nm on it, length is 10um.The LiCr of superficial growth carbon fiber
0.5Ga
0.5O
2The electrochemical property test of composite material the results are shown in table 1.
Embodiment 29
With 0.025mol Cr
2O
3, 0.09mol LiOH2H
2O, 0.025mol Al
2O
3With 0.01mol LiF be reactant, prepare LiCr according to embodiment 2 identical conditions
0.5Al
0.5O
1.9F
0.1Take by weighing 0.001mol Ni (NO
3)
26H
2O and 0.000015mol Cu (NO
3)
2.6H
2O adds the 100ml isopropyl alcohol, stirring and dissolving in beaker.Then with 10gLiCr
0.5Al
0.5O
1.9F
0.1Powder joins in this solution, stirred 5 hours at 25 ℃, by Buchner funnel or other filter plant with Separation of Solid and Liquid, then 100 ℃ of following vacuumizes 10 hours; The gained material is placed in the aluminium oxide boat, the tube furnace of packing into then, charge into argon gas, flow is 80sccm, after the temperature programming to 800 ℃, gas is converted to methane gas, total flow is 100sccm, and constant temperature was converted to argon gas with gas after carrying out chemical vapour deposition (CVD) in 24 hours, naturally cool to room temperature, products therefrom is the LiCr of superficial growth carbon fiber
0.5Al
0.5O
1.9F
0.1Composite material 29, average diameter of carbon fiber is 2nm on it, length is 50nm.Employing prepares electrode and test battery with embodiment 1 identical method.Its electrochemical property test the results are shown in table 1.
Embodiment 30
With 0.025mol Cr
2O
3, 0.08mol LiOH2H
2O, 0.025mol Al
2O
3With 0.01mol Li
2S is a reactant, prepares LiCr according to embodiment 2 identical conditions
0.5Al
0.5O
1.9S
0.1Take by weighing 0.0001mol Fe (NO
3)
26H
2O puts into beaker, adds the 100ml isopropyl alcohol, stirring and dissolving; Then with 10g LiCr
0.5Al
0.5O
1.9S
0.1Powder (average grain diameter is 200nm) joins in this solution, stirred 1 hour at 25 ℃, by Buchner funnel or other filter plant with Separation of Solid and Liquid, then 100 ℃ of following vacuumizes 10 hours; The gained material is placed in the aluminium oxide boat, the tube furnace of packing into then, charge into argon gas, flow is 80sccm, after the temperature programming to 600 ℃, gas is converted to acetylene gas, total flow is 100sccm, and constant temperature was converted to argon gas with gas after carrying out chemical vapour deposition (CVD) in 2 hours, naturally cool to room temperature, products therefrom is the LiCr of superficial growth carbon nano-tube
0.5Al
0.5O
1.9S
0.1Composite material, wherein the average diameter of carbon nano-tube is 50nm, length is 2um.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 31
With 0.025mol Cr
2O
3, 0.07mol LiOH2H
2O, 0.025mol Al
2O
3With 0.01mol Li
3N is a reactant, prepares LiCr according to embodiment 2 identical conditions (sintering atmosphere is N2)
0.5Al
0.5O
1.9N
0.1With embodiment 2, at LiCr
0.5Al
0.5O
1.9N
0.1Coated with carbon bed, the carbon that obtains having nucleocapsid structure coats LiCr
0.5Al
0.5O
1.9N
0.1Composite material 31.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 32
With 0.01mol Cr
2O
3, 0.1mol LiOH2H
2O, 0.04mol TiO
2And 0.04mol MgO is reactant, prepares Li[Cr according to embodiment 2 identical conditions
0.2Mg
0.4Ti
0.4] O
2With 50 gram Li[Cr
0.2Mg
0.4Ti
0.4] O
2With 2 gram conductive carbon blacks (particle diameter is 20nm), 5 gram starch mix, and adopt the method for mechanical ball milling, behind the ball milling 4 hours, under 300 ℃ of Ar gas, heating is 48 hours in the tube furnace, mechanical ball milling after 4 hours again after the cooling, cross 600 mesh sieves, powder after sieving is placed in the tube furnace once more, under Ar gas, is warming up to 700 ℃, switch to ethylene gas then, be incubated after 24 hours, cooling obtains the Li[Cr that the surface coats compound carbon-coating
0.2Mg
0.4Ti
0.4] O
2Composite material 32.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 33
With 0.02mol Cr
2O
3, 0.1mol LiOH2H
2O, 0.03mol SiO
2And 0.03mol SrO is reactant, prepares Li[Cr according to embodiment 2 identical conditions
0.4Sr
0.3Si
0.3] O
2With 50 gram Li[Cr
0.4Sr
0.3Si
0.3] O
2With 2 gram acetylene blacks (particle diameter is 40nm), 5 gram phenolic resins mix, and adopt the method for mechanical ball milling, behind the ball milling 4 hours, under 300 ℃ of Ar gas, heating is 48 hours in the tube furnace, mechanical ball milling after 4 hours again after the cooling, cross 600 mesh sieves, powder after sieving is placed in the tube furnace once more, under Ar gas, is warming up to 700 ℃, switch to ethylene gas then, be incubated after 24 hours, cooling obtains the Li[Cr that the surface coats compound carbon-coating
0.4Sr
0.3Si
0.3] O
2Composite material 33.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 34
With 0.015mol Cr
2O
3, 0.005mol V
2O
3, 0.005mol Mo
2O
3, 0.01mol Nb
2O
3, 0.02mol WO
2, 0.1mol LiOH2H
2O, 0.005mol Ca (OH)
2And 0.005mol ZrO
2Be reactant, prepare Li[Cr according to embodiment 2 identical conditions
0.3V
0.1Mo
0.1Nb
0.2W
0.2Ca
0.05Zr
0.05] O
2With 50 gram Li[Cr
0.3V
0.1Mo
0.1Nb
0.2W
0.2Ca
0.05Zr
0.05] O
2With 2 gram conductive carbon blacks (particle diameter is 20nm), 5 gram poly(ethylene oxide) mix, and adopt the method for mechanical ball milling, behind the ball milling 4 hours, under 600 ℃ of Ar gas, heating is 8 hours in the tube furnace, mechanical ball milling after 4 hours again after the cooling, cross 600 mesh sieves, powder after sieving is placed in the tube furnace once more, under Ar gas, is warming up to 800 ℃, switch to acetylene gas then, be incubated after 8 hours, cooling obtains the Li[Cr that the surface coats compound carbon-coating
0.3V
0.1Mo
0.1Nb
0.2W
0.2Ca
0.05Zr
0.05] O
2Composite material 34.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 35
With 0.02mol Cr
2O
3, 0.1mol LiOH2H
2O, 0.03mol ZnO and 0.03mol GeO
2Be reactant, prepare Li[Cr according to embodiment 2 identical conditions
0.4Zn
0.3Ge
0.3] O
2With 50 gram Li[Cr
0.2Mg
0.4Ti
0.4] O
2With 2 gram conductive carbon blacks (particle diameter is 20nm), 5 gram starch mix, and adopt the method for mechanical ball milling, behind the ball milling 4 hours, under 300 ℃ of Ar gas, heating is 48 hours in the tube furnace, mechanical ball milling after 4 hours again after the cooling, cross 600 mesh sieves, powder after sieving is placed in the tube furnace once more, under Ar gas, is warming up to 700 ℃, switch to ethylene gas then, be incubated after 24 hours, cooling obtains the surface and coats obtaining at Li[Cr of compound carbon-coating
0.4Zn
0.3Ge
0.3] O
2Coated with carbon bed, the carbon that obtains having nucleocapsid structure coats Li[Cr
0.4Zn
0.3Ge
0.3] O
2Composite material 30.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1
Embodiment 36
With 0.01mol Cr
2O
3, 0.08mol LiOH2H
2O, 0.04mol MgO, 0.04mol TiO
2With 0.02mol LiF be reactant, prepare Li[Cr according to embodiment 2 identical conditions
0.2Mg
0.4Ti
0.4] O
1.9F
0.2With 50 gram Li[Cr
0.2Mg
0.4Ti
0.4] O
1.9F
0.2With 2 gram conductive carbon blacks (particle diameter is 40nm), 5 gram Kynoar mix, and adopt the method for mechanical ball milling, behind the ball milling 4 hours, under 500 ℃ of Ar gas, heating is 4 hours in the tube furnace, mechanical ball milling after 4 hours again after the cooling, cross 600 mesh sieves, powder after sieving is placed in the tube furnace once more, under Ar gas, is warming up to 800 ℃, switch to ethylene gas then, be incubated after 24 hours, cooling obtains the Li[Cr that the surface coats compound carbon-coating
0.2Mg
0.4Ti
0.4] O
1.9F
0.2Composite material 36.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 37
With 0.01mol Cr
2O
3, 0.08mol LiOH2H
2O, 0.04mol MgO, 0.04mol TiO
2And 0.01molLi
2S is a reactant, prepares Li[Cr according to embodiment 2 identical conditions
0.2Mg
0.4Ti
0.4] O
1.9S
0.1With embodiment 2, at Li[Cr
0.2Mg
0.4Ti
0.4] O
1.9S
0.1Coated with carbon bed, the carbon that obtains having nucleocapsid structure coats Li[Cr
0.2Mg
0.4Ti
0.4] O
1.9S
0.1Composite material 37.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 38
With 0.01mol Cr
2O
3, 0.07mol LiOH2H
2O, 0.04mol MgO, 0.04mol TiO
2And 0.01molLi
3N is a reactant, and (sintering atmosphere is N according to embodiment 2 identical conditions
2) prepare Li[Cr
0.2Mg
0.4Ti
0.4] O
1.9N
0.1With embodiment 2, at Li[Cr
0.2Mg
0.4Ti
0.4] O
1.9N
0.1Composite material 38.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 39
With 0.01mol Cr
2O
3, 0.1mol LiOH2H
2O, 0.035mol MgO, 0.005mol Al
2O
3And 0.035molTiO
2Be reactant, prepare Li[Cr according to embodiment 2 identical conditions
0.2Mg
0.35Al
0.1Ti
0.35] O
2With embodiment 2, at Li[Cr
0.2Mg
0.35Al
0.1Ti
0.35] O
2Coated with carbon bed, the carbon that obtains having nucleocapsid structure coats Li[Cr
0.2Mg
0.35Al
0.1Ti
0.35] O
2Composite material 39.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 40
With 0.01mol Cr
2O
3, 0.1mol LiOH2H
2O, 0.001mol Ca (OH)
2, 0.078mol In (NO
3)
33H
2O and 0.001mol ZrO
2Be reactant, prepare Li[Cr according to embodiment 2 identical conditions
0.2Ca
0.01In
0.78Zr
0.01] O
2With embodiment 2, at Li[Cr
0.2Ca
0.01In
0.78Zr
0.01] O
2Coated with carbon bed, the carbon that obtains having nucleocapsid structure coats Li[Cr
0.2Ca
0.01In
0.78Zr
0.01] O
2Composite material 40.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 41
With 0.02mol Cr
2O
3, 0.1mol LiOH2H
2O, 0.015mol SrO, 0.015mol Ga
2O
3And 0.015molGeO
2Be reactant, prepare Li[Cr according to embodiment 2 identical conditions
0.4Sr
0.15Ga
0.3Ge
0.15] O
2With embodiment 2, at Li[Cr
0.4Sr
0.15Ga
0.3Ge
0.15] O
2Coated with carbon bed, the carbon that obtains having nucleocapsid structure coats Li[Cr
0.4Sr
0.15Ga
0.3Ge
0.15] O
2Composite material 41.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 42
With 0.045mol Cr
2O
3, 0.1mol LiOH2H
2O, 0.003mol MgO, 0.002mol Y
2O
3And 0.003molSiO
2Be reactant, prepare Li[Cr according to embodiment 2 identical conditions
0.9Mg
0.03Y
0.04Si
0.03] O
2With embodiment 2, at Li[Cr
0.9Mg
0.03Y
0.04Si
0.03] O
2Coated with carbon bed, the carbon that obtains having nucleocapsid structure coats Li[Cr
0.9Mg
0.03Y
0.04Si
0.03] O
2Composite material 42.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 43
With 0.015mol Cr
2O
3, 0.1mol LiOH2H
2O, 0.01mol Ca (OH)
2, 0.05mol Sc (NO
3)
3With 0.01mol ZrO
2Be reactant, prepare Li[Cr according to embodiment 2 identical conditions
0.3Ca
0.1Sc
0.5Zr
0.1] O
2With embodiment 2, at Li[Cr
0.3Ca
0.1Sc
0.5Zr
0.1] O
2Coated with carbon bed, the carbon that obtains having nucleocapsid structure coats Li[Cr
0.3Ca
0.1Sc
0.5Zr
0.1] O
2Composite material 43.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 44
With 0.025mol Cr
2O
3, 0.08mol LiOH2H
2O, 0.01mol MgO, 0.015mol La
2O
3, 0.01molTiO
2With 0.02mol LiF be reactant, prepare Li[Cr according to embodiment 2 identical conditions
0.5Mg
0.1La
0.3Ti
0.1] O
1.9F
0.2With embodiment 2, at Li[Cr
0.5Mg
0.1La
0.3Ti
0.1] O
1.9F
0.2Coated with carbon bed, the carbon that obtains having nucleocapsid structure coats Li[Cr
0.5Mg
0.1La
0.3Ti
0.1] O
1.9F
0.2Composite material 44.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1
Embodiment 45
With 0.025mol Cr
2O
3, 0.08mol LiOH2H
2O, 0.01mol MgO, 0.015mol Al
2O
3, 0.01molTiO
2With 0.01mol Li
2S is a reactant, prepares Li[Cr according to embodiment 2 identical conditions
0.5Mg
0.1Al
0.3Ti
0.1] O
1.9S
0.1With embodiment 2, at Li[Cr
0.5Mg
0.1Al
0.3Ti
0.1] O
1.9S
0.1Coated with carbon bed, the carbon that obtains having nucleocapsid structure coats Li[Cr
0.5Mg
0.1Al
0.3Ti
0.1] O
1.9S
0.1Composite material 45.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
Embodiment 46
With 0.025mol Cr
2O
3, 0.07mol LiOH2H
2O, 0.01mol MgO, 0.015mol Al
2O
3, 0.01molTiO
2With 0.01mol Li
3N is a reactant, and (sintering atmosphere is N according to embodiment 2 identical conditions
2) prepare Li[Cr
0.5Mg
0.1Al
0.3Ti
0.1] O
1.9N
0.1With embodiment 2, at Li[Cr
0.5Mg
0.1Al
0.3Ti
0.1] O
1.9N
0.1Coated with carbon bed, the carbon that obtains having nucleocapsid structure coats Li[Cr
0.5Mg
0.1Al
0.3Ti
0.1] O
1.9N
0.1Composite material 46.Employing prepares electrode and test battery with embodiment 1 identical method.Its coating layer parameter and electrochemical property test the results are shown in table 1.
The composition of the lamina-structure lithium-contained composite metal oxide of table 1, coated with carbon of the present invention and chemical property
| Sequence number | Lamina-structure lithium-contained composite metal oxide carbon clad composite material | Chemical property | ||||
| Li[Cr xLi (1/3-x/3)M (2/3-2x/3)]O 2-yX z | Carbon coating layer | Reversible capacity | Starting efficiency | 50 all capacity | ||
| Content | Thickness | |||||
| wt％ | μm | mAh/g | ％ | mAh/g | ||
| 1 | Li[Cr 0.2Li 0.267Si 0.533]O 2 | 0.1 | 0.002 | 120 | 80 | 115 |
| 2 | Li[Cr 0.2Li 0.267Si 0.533]O 2 | 5 | 1 | 140 | 82 | 135 |
| 3 | Li[Cr 0.4Li 0.2Si 0.4]O 2 | 5 | 1 | 180 | 85 | 170 |
| 4 | Li[Cr 0.9Li 0.033Si 0.067]O 2 | 10 | 5 | 140 | 70 | 130 |
| 5 | Li[V 0.2Li 0.267Ge 0.533]O 2 | 3 | 0.5 | 128 | 72 | 105 |
| 6 | Li[Cr 0.4Na 0.2Ge 0.4]O 2 | 5 | 2 | 195 | 86 | 185 |
| 7 | Li[V 0.9Na 0.033Ge 0.067]O 2 | 8 | 3 | 175 | 84 | 168 |
| 8 | Li[Cr 0.2Na 0.267Zr 0.533]O 2 | 8 | 3 | 142 | 80 | 128 |
| 9 | Li[Cr 0.4Na 0.2Zr 0.4]O 2 | 5 | 2 | 200 | 85 | 185 |
| 10 | Li[Cr 0.9Na 0.033Zr 0.067]O 2 | 5 | 2 | 140 | 70 | 110 |
| 11 | Li[Cr 0.4Li 0.2Ti 0.4]O 2 | 10 | 5 | 205 | 85 | 195 |
| 12 | Li[Cr 0.3Li 0.233Ti 0.467]O 2 | 5 | 2 | 165 | 82 | 150 |
| 13 | Li[Nb 0.4Li 0.2Ti 0.2Zr 0.2]O 2 | 5 | 2 | 195 | 82 | 190 |
| 14 | Li[Cr 0.4Li 0.2Ti 0.3Si 0.1]O 2 | 5 | 2 | 165 | 75 | 145 |
| 15 | Li[Cr 0.4Li 0.2Ti 0.2Zr 0.1Ge 0.1]O 2 | 5 | 2 | 155 | 73 | 140 |
| 16 | Li[Cr 0.4Li 0.2Ti 0.1Zr 0.1Ge 0.1Si 0.1] O 2 | 4 | 1 | 180 | 81 | 168 |
| 17 | Li[Cr 0.4Li 0.2Zr 0.4]O 1.9F 0.1 | 5 | 2 | 182 | 87 | 175 |
| 18 | Li[Mo 0.4Li 0.2Zr 0.4]O 1.9F 0.2 | 5 | 2 | 145 | 70 | 110 |
| 19 | Li[Cr 0.4Li 0.2Zr 0.4]O 1.9S 0.1 | 5 | 2 | 184 | 74 | 173 |
| 20 | Li[V 0.4Li 0.2Zr 0.4]O 1.9N 0.1 | 5 | 2 | 136 | 71 | 110 |
| 21 | LiCr 0.2Al 0.8O 2 | 10 | 5 | 160 | 89 | 155 |
| 22 | LiCr 0.5Al 0.5O 2 | 20 | 10 | 210 | 86 | 188 |
| 23 | LiCr 0.9Al 0.1O 2 | 5 | 3 | 172 | 90 | 165 |
| 24 | LiCr 0.5Sc 0.5O 2 | 6 | 4 | 178 | 89 | 162 |
| 25 | LiCr 0.5Y 0.5O 2 | 5 | / | 186 | 90 | 175 |
| 26 | LiCr 0.9La 0.1O 2 | 5 | / | 182 | 91 | 168 |
| 27 | LiCr 0.5Ga 0.5O 2 | 5 | / | 178 | 92 | 166 |
| 28 | LiCr 0.5In 0.5O 2 | 10 | / | 136 | 94 | 128 |
| 29 | LiCr 0.5Al 0.5O 1.9F 0.1 | 0.1 | / | 215 | 93 | 208 |
| 30 | LiCr 0.5Al 0.5O 1.9S 0.1 | 3 | / | 210 | 91 | 205 |
| 31 | LiCr 0.5Al 0.5O 1.9N 0.1 | 5 | / | 190 | 91 | 188 |
| 32 | Li[Cr 0.2Mg 0.4Ti 0.4]O 2 | 2 | 0.5 | 164 | 94 | 148 |
| 33 | Li[Cr 0.4Sr 0.3Si 0.3]O 2 | 5 | 2 | 178 | 92 | 168 |
| 34 | Li[Cr 0.3V 0.1Mo 0.1Nb 0.2W 0.2Ca 0.05Zr 0.05]O 2 | 7 | 2 | 162 | 92 | 156 |
| 35 | Li[Cr 0.4Zn 0.3Ge 0.3]O 2 | 6 | 4 | 174 | 93 | 164 |
| 36 | Li[Cr 0.2Mg 0.4Ti 0.4]O 1.9F 0.2 | 8 | 5 | 148 | 90 | 120 |
| 37 | Li[Cr 0.2Mg 0.4Ti 0.4]O 1.9S 0.1 | 5 | 3 | 138 | 93 | 126 |
| 38 | Li[Cr 0.2Mg 0.4Ti 0.4]O 1.9N 0.1 | 5 | 3 | 140 | 93 | 132 |
| 39 | Li[Cr 0.2Mg 0.35Al 0.1Ti 0.35]O 2 | 4 | 2 | 136 | 90 | 128 |
| 40 | Li[Cr 0.2Ca 0.01In 0.78Zr 0.01]O 2 | 4 | 3 | 100 | 91 | 94 |
| 41 | Li[Cr 0.4Sr 0.15Ga 0.3Ge 0.15]O 2 | 4 | 3 | 184 | 92 | 148 |
| 42 | Li[Cr 0.9Mg 0.03Y 0.04Si 0.03]O 2 | 4 | 3 | 210 | 94 | 188 |
| 43 | Li[Cr 0.3Ca 0.1Sc 0.5Zr 0.1]O 2 | 4 | 3 | 185 | 92 | 168 |
| 44 | Li[Cr 0.5Mg 0.1La 0.3Ti 0.1]O 1.9F 0.2 | 4 | 3 | 192 | 90 | 182 |
| 45 | Li[Cr 0.5Mg 0.1Al 0.3Ti 0.1]O 1.9S 0.1 | 4 | 3 | 177 | 86 | 162 |
| 46 | Li[Cr 0.5Mg 0.1Al 0.3Ti 0.1]O 1.9N 0.1 | 4 | 3 | 193 | 85 | 183 |
Claims (10)
1, a kind of lamina-structure lithium-contained composite metal oxide of coated with carbon, it is the composite material of a nucleocapsid structure, core material is the lithium-contained composite metal oxide particle with layer structure, is " shell " that a coating carbon-coating forms on its surface.
2, the lamina-structure lithium-contained composite metal oxide of coated with carbon as claimed in claim 1, it is characterized in that: the architectural feature of the lithium-contained composite metal oxide of described layer structure as core material is: on perpendicular to the c direction of principal axis in the crystal structure, and alternately arranging successively oxygen atomic layer, lithium atom layer, oxygen atomic layer, metal level and oxygen atomic layer; Wherein, in the metal level for being selected from active element Cr, V, Nb, Mo, one or more in W and the nonactive element M, and the total chemical valence of each element of metal level is 3, satisfies electroneutral requirement;
The element of described nonactive element M for appraising at the current rate in charge and discharge process comprises that chemical valence is the Li and the Na of monovalence, and chemical valence is the Mg of divalence, and Ca, Sr and Zn, chemical valence are the Al of trivalent, Ga, and Sc, Y, La, chemical valence are the Ti of tetravalence, Zr, Si, Ge.
3, the lamina-structure lithium-contained composite metal oxide of coated with carbon as claimed in claim 1 is characterized in that: the chemical formula of the lithium-contained composite metal oxide of described layer structure is Li[M
0 xM
1 (1/2-x/2)M
2 (1/2-x/2)] O
2-yX
z
Wherein, M
0For being selected from Cr, V, Nb, Mo, one or more among the W;
M
1For being selected from Mg, Ca, Sr, one or more among the Zn;
M
2For being selected from Ti, Zr, Si, one or more among the Ge;
X is for being selected from F, S, one or more among the N;
0.2≤x≤0.9，0≤y≤0.1，0≤z≤0.2。
4, the lamina-structure lithium-contained composite metal oxide of coated with carbon as claimed in claim 1 is characterized in that: the chemical formula of the lithium-contained composite metal oxide of described layer structure is Li[M
0 xM
1 (1/3-1 x/3)M
2 (2/3-2x/3)] O
2-yX
z
Wherein, M
0For being selected from Cr, V, Nb, Mo, one or more among the W;
M
1For Li or/and Na;
M
2For being selected from Ti, Zr, Si, one or more among the Ge;
X is for being selected from F, S, one or more among the N;
0.2≤x≤0.9，0≤y≤0.1，0≤z≤0.2。
5, the lamina-structure lithium-contained composite metal oxide of coated with carbon as claimed in claim 1 is characterized in that: the chemical formula of the lithium-contained composite metal oxide of described layer structure is LiM
0 xM
1-xO
2-yX
z
Wherein, M
0For being selected from Cr, V, Nb, Mo, one or more among the W;
M is for being selected from Al, Ga, Sc, Y, La, one or more among the In;
X is for being selected from F, S, one or more among the N;
0.2≤x≤0.9，0≤y≤0.1，0≤z≤0.2。
6, the lamina-structure lithium-contained composite metal oxide of coated with carbon as claimed in claim 1 is characterized in that: the chemical formula of the lithium-contained composite metal oxide of described layer structure is
Li[M
0 xM
1 (1/2-x/2-w/2)M
2 wM
3 (1/2-x/2-w/2)]O
2-yX
z
M wherein
0For being selected from Cr, V, Nb, Mo, one or more among the W;
M
1For being selected from Mg, Ca, Sr, one or more among the Zn;
M
2For being selected from Al, Ga, Sc, Y, La, one or more among the In;
M
3For being selected from Ti, Zr, Si, one or more among the Ge;
X is for being selected from F, S, one or more among the N;
0.2≤x≤0.9，0＜w＜0.8，0≤y≤0.1，0≤z≤0.2。
7, the lamina-structure lithium-contained composite metal oxide of coated with carbon as claimed in claim 1 is characterized in that: " shell " that described coating carbon-coating forms, form by the carbon of disordered structure, thickness is the carbon-coating of 2 nm～5 μ m; The percentage by weight that this carbon-coating material accounts for whole composite material is 0.1～10 wt%.
8, the lamina-structure lithium-contained composite metal oxide of coated with carbon as claimed in claim 1, it is characterized in that: " shell " that described coating carbon-coating forms, form by the hard carbon of conductive carbon particle and continuous disordered structure, thickness is the compound carbon-coating of 10 nm～10 μ m; The percentage by weight that this compound carbon-coating accounts for whole composite material is 0.1～20wt%.Wherein, described conductive carbon particle is a carbon black, acetylene black, and spherical graphite, diameter are 2nm～2 μ m.
9, the lamina-structure lithium-contained composite metal oxide of coated with carbon as claimed in claim 1, it is characterized in that: " shell " that described coating carbon-coating forms is that one that be made up of carbon nano-tube or carbon nano-fiber, thickness (being carbon nano-tube or carbon nano-fiber length) is the carbon-coating of 50nm～10 μ m; The percentage by weight that this carbon-coating material accounts for whole composite material is 0.1～10 wt%.Wherein, the diameter of described carbon nano-tube or nanofiber is 2～500nm, and the caliber of carbon nano-tube is 1～20 nm.
10, the lamina-structure lithium-contained composite metal oxide of coated with carbon as claimed in claim 1 is as the purposes of the positive electrode active materials of serondary lithium battery.
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