CN108832106A - A kind of redox graphene-cobalt nickel oxide aluminium lithium composite positive pole, preparation method and its application - Google Patents
A kind of redox graphene-cobalt nickel oxide aluminium lithium composite positive pole, preparation method and its application Download PDFInfo
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Abstract
The present invention provides a kind of redox graphene-cobalt nickel oxide aluminium lithium composite positive pole, preparation method and its application, composite positive pole includes the material with structure shown in formula I of redox graphene and redox graphene cladding：LiNixCoyAl1‑x‑yO2Formula I；0.8<x<1,0.01<y<0.2.The material has the material of structure shown in formula I by using inert matter graphene coated, and electric conductivity improves, so that higher discharge capacity for the first time and cycle performance are made it have, high rate performance and thermal stability also with higher.At 2.7~4.3V, 0.1C electric current, material first discharge specific capacity reaches 215.8mAhg‑1, coulombic efficiency is 91.01% for the first time；It is recycled 200 weeks under 1C electric current, for capacity retention ratio 85.6%, graphene Y-oxides doping cobalt aluminium lithium composite positive pole can effectively improve the absorption peak temperature of material.
Description
Technical field
The invention belongs to lithium battery material technical field more particularly to a kind of redox graphene-cobalt nickel oxide aluminium lithiums
Composite positive pole, preparation method and its application.
Background technique
From Sony in nineteen ninety at first by lithium ion battery functionization, until being constantly subjected to greatly pay close attention to today.Lithium
Ion battery because its energy density is high, has extended cycle life, self discharge degree is small, memory-less effect, environmental-friendly the features such as due to obtain
To being widely used in electric tool, digital product and Medical Devices etc..Lithium ion battery mainly by positive and negative pole material,
The part such as diaphragm, electrolyte composition, and positive electrode is the most crucial portion for determining lithium ion battery overall performance and cost
/ mono-, characteristic, which has energy density, cycle life, safety of battery etc., to be directly affected, so its research and progress
It is constantly subjected to the extensive concern of scientific circles.
With the continuous development of information age, higher requirement is also produced to the properties of lithium ion battery.Currently,
The most nickel cobalt lithium aluminate LiNi of the predominantly rich ni-type of the tertiary cathode material of commercial valuexCoyAl1-x-y02(0.8<x<1,0.01
<y<0.2) LiCoO, is combined2Stability, LiNiO2High capacity the advantages that, have high specific capacity, be replace
LiCoO2Most ideal material, it has also become one of the research emphasis of power battery industry in recent years.
But with the increase of nickel content, so that its comprehensive performance Shortcomings:1. the nickel cobalt aluminium under high de- lithium state
(NCA) there is the unstable Ni of high concentration4+Ion can generate more stable NiO in NCA material surface, hinder material surface
Anti- increase reduces capacity.2. surface can rapidly absorb NCA positive electrode as other rich nickel system positive electrodes in air
Water and carbon dioxide and generate lithium hydroxide and lithium carbonate, wherein lithium hydroxide can react generation with electrolyte lithium hexafluoro phosphate
HF.A kind of effective way for the chemical property and thermal stability that improve rich ni-type positive electrode is in NCA positive electrode
One layer of inactive nanometer layer is coated, these clads can effectively reduce active material and contact with the direct of electrolyte, mitigate
Its electrolytic corrosion being subject to, while the dissolution of bulk material metal ion is decreased, maintain material in charge and discharge process
Stable structure.But if doing so, electric conductivity and Shortcomings.Therefore, it is necessary to explore the side that can effectively solve the above problem
Method seems increasingly important.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of redox graphene-cobalt nickel oxide aluminium lithium anode composites
Material, preparation method and its application, composite positive pole capacity with higher and cycle performance.
The present invention provides a kind of redox graphene-cobalt nickel oxide aluminium lithium composite positive poles, including reduction-oxidation
The material with structure shown in formula I of graphene and redox graphene cladding：
LiNixCoyAl1-x-yO2Formula I；
Wherein, 0.8<x<1,0.01<y<0.2.
Preferably, the mass ratio of the redox graphene and the material with structure shown in formula I is 0.5~5:95~
99.5。
Preferably, described 0.8<x<0.85；0.12<y<0.2.
Preferably, the x=0.815；Y=0.15.
The present invention provides a kind of redox graphene described in above-mentioned technical proposal-cobalt nickel oxide aluminium lithium anode composite materials
The preparation method of material, includes the following steps：
It is mixed after redox graphene is dispersed in a solvent with the material with structure shown in formula I, obtains oxygen reduction fossil
Black alkene-cobalt nickel oxide aluminium lithium composite positive pole；
LiNixCoyAl1-x-yO2Formula I；
Wherein, 0.8<x<1,0.01<y<0.2.
Preferably, the mixed temperature is 50~80 DEG C, and the mixed time is 2~8h；
Preferably, the solvent is selected from N-Methyl pyrrolidone, acetone, espeleton, methylisobutylketone, toluene and diformazan
One of benzene is a variety of.
Preferably, the redox graphene is made by following methods：
After graphene oxide is prepared according to Hummers method, restores, restored in hydrogen and nitrogen mixture atmosphere
Graphene oxide.
Preferably, the material with structure shown in formula I is made in accordance with the following methods：
Nickel salt, cobalt salt, aluminium salt and water are mixed, adjust pH value to 10~13, reaction obtains nickel cobalt lithium aluminate cathode material
Presoma；
After the nickel cobalt lithium aluminate cathode material presoma and lithium salts are mixed, calcines, had under oxygen atmosphere
The material of structure shown in formula I.
The present invention provides a kind of lithium ion batteries, including redox graphene-nickel oxide described in above-mentioned technical proposal
Redox graphene-cobalt nickel oxide aluminium lithium of the preparation of preparation method described in cobalt aluminium lithium composite positive pole or above-mentioned technical proposal
Composite positive pole.
The present invention provides a kind of redox graphene-cobalt nickel oxide aluminium lithium composite positive poles, including reduction-oxidation
The material with structure shown in formula I of graphene and redox graphene cladding：LiNixCoyAl1-x-yO2Formula I；Wherein, 0.8<
x<1,0.01<y<0.2.The composite positive pole has structure shown in formula I by using inert matter redox graphene cladding
Material, electric conductivity improve, to make it have higher discharge capacity for the first time and cycle performance.The composite positive pole also has
There are higher high rate performance and thermal stability.The experimental results showed that：Under 2.7~4.3V voltage, 0.1C electric current, anode composite material
Material first discharge specific capacity reaches 215.8mAhg-1, coulombic efficiency is 91.01% for the first time；It is recycled 200 weeks under 1C electric current, capacity
Conservation rate is 85.6%；Under 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C current density, the specific capacity of composite positive pole
Respectively 215.8mAhg-1、190.4mAh·g-1、181.6mAh·g-1、171.2mAh·g-1、160.1mAh·g-1、
154.5mAh·g-1And 135.3mAhg-1；Graphene Y-oxides doping cobalt aluminium lithium composite positive pole can be improved effectively
The absorption peak temperature (264 DEG C of 256 DEG C of vs) of material, shows that the stability of material is improved.
Detailed description of the invention
Fig. 1 is the scanning of redox graphene@cobalt nickel oxide aluminium lithium composite positive pole prepared by the embodiment of the present invention 1
Electron microscope；
Fig. 2 is the redox graphene@cobalt nickel oxide aluminium lithium composite positive pole preparation that the embodiment of the present invention 1 provides
Cycle performance of battery test chart；
Fig. 3 is the redox graphene@cobalt nickel oxide aluminium lithium composite positive pole and blank that the embodiment of the present invention 1 provides
The high rate performance figure of group nickel cobalt lithium aluminate cathode material；
Fig. 4 is the redox graphene@cobalt nickel oxide aluminium lithium composite positive pole and blank that the embodiment of the present invention 1 provides
The heat stability testing figure of group nickel cobalt lithium aluminate cathode material.
Specific embodiment
The present invention provides a kind of redox graphene-cobalt nickel oxide aluminium lithium composite positive poles, including reduction-oxidation
The material with structure shown in formula I of graphene and redox graphene cladding：
LiNixCoyAl1-x-yO2Formula I；
Wherein, 0.8<x<1,0.01<y<0.2.
Redox graphene provided by the invention-cobalt nickel oxide aluminium lithium composite positive pole is by using inert matter
Redox graphene cladding has the material of structure shown in formula I, and electric conductivity improves, to make it have higher discharge capacity for the first time
And cycle performance.Composite positive pole high rate performance also with higher and thermal stability.The surface of composite positive pole is
One layer of redox graphene is inactive substance, can effectively reduce the direct of material with structure shown in formula I and electrolyte
Contact, mitigates its electrolytic corrosion being subject to, while decreasing the dissolution of metal ion in positive electrode, maintains anode composite
Stable structure of the material in charge and discharge process.
Redox graphene provided by the invention-cobalt nickel oxide aluminium lithium composite positive pole includes reduction-oxidation graphite
Alkene.The redox graphene preferably by the way that graphene oxide is prepared according to Hummers method after, it is mixed in hydrogen and nitrogen
It closes to restore in atmosphere and obtain.
Redox graphene provided by the invention-cobalt nickel oxide aluminium lithium composite positive pole includes the oxygen reduction fossil
The material with structure shown in formula I of black alkene cladding：
LiNixCoyAl1-x-yO2Formula I.
The material with structure shown in formula I is denoted as cobalt nickel oxide aluminium lithium material.
Wherein, 0.8<x<1；Preferably, 0.8<x<0.85；It is highly preferred that 0.81<x<0.82.
0.01<y<0.2；Preferably, 0.12<y<0.2；It is highly preferred that 0.14<y<0.16.
In the specific embodiment of the invention, the x=0.815；Y=0.15.
In the present invention, the mass ratio of the redox graphene and the material with structure shown in formula I is preferably 0.5~5:
95~99.5.In the specific embodiment of the invention, the mass ratio of the redox graphene and the material with structure shown in formula I is
0.5：99.5,1:99 or 5:95.
The present invention provides a kind of redox graphene described in above-mentioned technical proposal-cobalt nickel oxide aluminium lithium anode composite materials
The preparation method of material, includes the following steps：
It is mixed after redox graphene is dispersed in a solvent with the material with structure shown in formula I, obtains graphene-oxidation
Nickel cobalt aluminium lithium composite positive pole；
LiNixCoyAl1-x-yO2Formula I；
Wherein, 0.8<x<1,0.01<y<0.2.
In the present invention, the redox graphene is preferably made in accordance with the following methods：
After graphene oxide is prepared according to Hummers method, restores, restored in hydrogen and nitrogen mixture atmosphere
Graphene oxide.
Hydrogen preferably accounts for the 5~10% of mixed atmosphere volume in the hydrogen and nitrogen mixture atmosphere.
In the present invention, the material with structure shown in formula I is preferably made in accordance with the following methods：
Nickel salt, cobalt salt, aluminium salt and water are mixed, adjust pH value to 10~13, reaction obtains nickel cobalt lithium aluminate cathode material
Presoma；
After the nickel cobalt lithium aluminate cathode material presoma and lithium salts are mixed, calcines, had under oxygen atmosphere
The material of structure shown in formula I.
The present invention mixes nickel salt, cobalt salt, aluminium salt and water, adjusts pH value to 10~13, reaction is obtaining nickel cobalt lithium aluminate just
Pole material precursor.The nickel salt, cobalt salt, aluminium salt and water mixing preferably carry out under stirring conditions；The rate of the stirring
Preferably 300~600rpm；The time of the stirring is preferably 0.5~5h.
In the present invention, the nickel salt is preferably selected from one of nickel acetate, nickel sulfate, nickel nitrate and nickel chloride or more
Kind；
The cobalt salt is preferably selected from one of cobalt acetate, cobaltous sulfate, cobalt nitrate and cobalt chloride or a variety of；
The aluminium salt is preferably selected from one of aluminum nitrate, aluminum sulfate and aluminium chloride or a variety of.
The water is preferably selected from deionized water.
In the present invention, the molar ratio of the nickel salt, cobalt salt and aluminium salt is preferably 80~85:10~15:5.The nickel salt,
The amount of the total material of cobalt salt and aluminium salt and the molal volume ratio of water are 1mol:(2~10) L.
The present invention preferably mixes nickel salt, cobalt salt, aluminium salt and water under an inert atmosphere；The inert atmosphere is preferably argon gas.
Present invention preferably employs lye to adjust pH value to 10~13；The lye is preferably selected from the mixed liquor of sodium hydroxide and ammonium hydroxide, institute
The volume ratio for stating sodium hydroxide and ammonium hydroxide is preferably 1~99:99~1.
After obtaining nickel cobalt lithium aluminate cathode material presoma, the present invention by the nickel cobalt lithium aluminate cathode material presoma and
After lithium salts mixing, is calcined under oxygen atmosphere, obtain the material with structure shown in formula I.In the present invention, the lithium salts preferably is selected from hydrogen
One of lithia, lithium carbonate and lithium nitrate are a variety of；More preferable lithium hydroxide.The nickel cobalt lithium aluminate cathode material forerunner
The mass ratio of the material of body and lithium salts is preferably 1:0.5~1.1；In the specific embodiment of the invention, the nickel cobalt lithium aluminate anode
The mass ratio of the material of material precursor and lithium salts is 1:1.05.
The present invention preferably mixes the nickel cobalt lithium aluminate cathode material in ball mill by wet process well known to those skilled in the art
Presoma and lithium salts；Dehydrated alcohol is preferably added to when ball milling.What the nickel cobalt lithium aluminate cathode material presoma and lithium salts mixed
Time is preferably 2~4h；In a particular embodiment, the time of nickel cobalt lithium aluminate cathode material presoma and lithium salts mixing is 4h.
The present invention is preferably first dried after ball milling to calcine again.In the present invention, the temperature of the calcining is preferably 700~800 DEG C,
The time of the calcining is preferably 10~30h；The heating rate of the calcining is preferably 2~5 DEG C/min.Present invention preferably employs
Calcine by steps mode；It is preferred that being first warming up to 500~600 DEG C, 3~10h is kept the temperature；It is warming up to 600~800 DEG C again, heat preservation 10~
20h。
In the present invention, the redox graphene is preferably dispersed in a solvent by the way of ultrasound；The ultrasound
Time be preferably 1~2h.After the redox graphene disperses in a solvent and the material with structure shown in formula I mixing temperature
Preferably 50~80 DEG C of degree, the time is 2~8h.
In the present invention, the mass ratio of the cobalt nickel oxide aluminium lithium anode material presoma and redox graphene is preferred
It is 95~99.5:0.5~5.
The present invention provides a kind of lithium ion batteries, including prepare described in above-mentioned technical proposal or described in above-mentioned technical proposal
Redox graphene-cobalt nickel oxide aluminium lithium composite positive pole of method preparation.
In order to further illustrate the present invention, below with reference to embodiment to a kind of redox graphene-provided by the invention
Cobalt nickel oxide aluminium lithium composite positive pole, preparation method and its application are described in detail, but cannot be interpreted as them
Limiting the scope of the present invention.
Embodiment 1
1), by nickel nitrate, cobalt nitrate and aluminum nitrate with molar ratio 0.815:0.15:0.035 is dissolved in deionized water and mixing
Uniformly, injection is full of in the continuous stirred tank reactor of argon gas, is then slowly dropped into sodium hydroxide and the control of ammonium hydroxide mixed alkali liquor is molten
Nickel cobalt lithium aluminate cathode material presoma is made with the progress of reaction in liquid pH value 10；
2), by cobalt lithium aluminate cathode material presoma and lithium hydroxide with 1:It is added after 1.05 molar ratio mixing appropriate
Dehydrated alcohol carries out ball milling 4h, drying；Taking-up is placed in high-temperature calcination stove 750 DEG C of calcining 12h (heating rates 5 under oxygen
DEG C/min, and 550 DEG C, soaking time 4h are warming up to, then be warming up to 750 DEG C, soaking time 12h), obtain cobalt nickel oxide lithium aluminate material
Material；
3) after graphene oxide, is prepared using Hummers method, under the nitrogen atmosphere containing 5% hydrogen at 500 DEG C,
4h is restored, redox graphene is obtained；
4) it, by graphene ultrasonic disperse 2h in N-Methyl pyrrolidone obtained by step 3), then will be aoxidized obtained by step 2)
(mass ratio of the cobalt nickel oxide aluminium lithium material of the step 2) and redox graphene is 99.5 to nickel cobalt aluminium lithium material:0.5)
It is added, after 50 DEG C of heating 8h, is dried in 80 DEG C of vacuum oven, redox graphene@cobalt nickel oxide aluminium lithium is made
Composite positive pole, wherein the chemical molecular formula of cobalt nickel oxide lithium material is LiNi0.815Co0.15Al0.035O2。
Fig. 1 is the SEM of redox graphene@cobalt nickel oxide aluminium lithium composite positive pole prepared by the embodiment of the present invention 1
Figure；As can be seen from Figure 1：Redox graphene is uniformly coated on nickel cobalt aluminic acid lithium material microparticle surfaces.
Fig. 2 is the redox graphene@cobalt nickel oxide aluminium lithium composite positive pole preparation that the embodiment of the present invention 1 provides
Cycle performance of battery test chart；As can be known from Fig. 2, under 1C current density, specific discharge capacity is above-mentioned composite positive pole
175.6mAh/g；Obtained redox graphene@cobalt nickel oxide aluminium lithium composite positive pole is in 2.7V~4.3V, 1C electric current
Lower circulation 200 weeks, capacity retention ratio is 85.6%.However blank group NCA capacity retention ratio is only 73.4%.Illustrate reduction-oxidation
Graphene@cobalt nickel oxide aluminium lithium composite positive pole cycle performance is improved.
Fig. 3 is the redox graphene@cobalt nickel oxide aluminium lithium composite positive pole and blank that the embodiment of the present invention 1 provides
The high rate performance figure of group nickel cobalt lithium aluminate cathode material；Wherein, a is that nickel bores aluminium lithium anode material, and b is redox graphene@
Cobalt nickel oxide aluminium lithium composite positive pole (rGO@LNCAO)；As can be known from Fig. 3, in 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and
Under 10C current density, modified NCA specific capacity is respectively 215.8mAhg-1,190.4mAh·g-1,181.6mAh·g-1,
171.2mAh·g-1, 160.1mAhg-1,154.5mAh·g-1And 135.3mAhg-1, however blank group NCA only has
201mAh·g-1,189.5mAh·g-1,181.3mAh·g-1,167.5mAh·g-1,151.1mAh·g-1,136mAh·g-1With
117.8mAh·g-1.Show that battery high rate performance and cycle performance after being modified have significantly to be promoted.
Fig. 4 is the redox graphene@cobalt nickel oxide aluminium lithium composite positive pole that the embodiment of the present invention 1 provides
The heat stability testing figure of (LNCAO rGO) and blank group nickel cobalt lithium aluminate cathode material (LNCAO)；Wherein ■ is LNCAO@
The thermostabilization curve of rGO,For the thermostabilization curve of LNCAO；As can be seen from Figure 4：Under identical testing conditions, graphene adulterates
Cobalt nickel oxide aluminium lithium composite positive pole can effectively improve the absorption peak temperature (264 DEG C of 256 DEG C of vs) of material, show material
The stability of material is improved.
Embodiment 2
1), by nickel nitrate, cobalt nitrate and aluminum nitrate with molar ratio 0.815:0.15:0.035 is dissolved in deionized water and mixing
Uniformly, injection is full of in the continuous stirred tank reactor of argon gas, is then slowly dropped into sodium hydroxide and the control of ammonium hydroxide mixed alkali liquor is molten
Nickel cobalt lithium aluminate cathode material presoma is made with the progress of reaction in liquid pH value 11；
2), by cobalt lithium aluminate cathode material presoma and lithium hydroxide with 1:It is added after 1.05 molar ratio mixing appropriate
Dehydrated alcohol carries out ball milling 4h, drying；Taking-up is placed in high-temperature calcination stove 750 DEG C of calcining 12h (heating rates 5 under oxygen
DEG C/min, and 550 DEG C, soaking time 4h are warming up to, then be warming up to 750 DEG C, soaking time 12h), obtain cobalt nickel oxide lithium aluminate material
Material；
3) after graphene oxide, is prepared using Hummers method, under the nitrogen atmosphere containing 5% hydrogen at 500 DEG C,
4h is restored, redox graphene is obtained；
4), by redox graphene ultrasonic disperse 2h in N-Methyl pyrrolidone obtained by step 3), then by step 2)
(the cobalt nickel oxide aluminium lithium material of the step 2) and the mass ratio of redox graphene are gained cobalt nickel oxide aluminium lithium material
99.5:0.5) it is added, after 50 DEG C of heating 8h, is dried in 80 DEG C of vacuum oven, graphene@cobalt nickel oxide aluminium lithium is made
Composite positive pole, wherein the chemical molecular formula of cobalt nickel oxide aluminium lithium material is LiNi0.815Co0.15Al0.035O2。
Embodiment 3
1), by nickel nitrate, cobalt nitrate and aluminum nitrate with molar ratio 0.815:0.15:0.035 is dissolved in deionized water and mixing
Uniformly, injection is full of in the continuous stirred tank reactor of argon gas, is then slowly dropped into sodium hydroxide and ammonium hydroxide mixed alkali liquor controls pH value of solution
Nickel cobalt lithium aluminate cathode material presoma is made with the progress of reaction in value 10；
2), by cobalt lithium aluminate cathode material presoma and lithium hydroxide with 1:It is added after 1.05 molar ratio mixing appropriate
Dehydrated alcohol carries out ball milling 4h, drying；Taking-up is placed in high-temperature calcination stove 750 DEG C of calcining 12h (heating rates 5 under oxygen
DEG C/min, and 550 DEG C, soaking time 4h are warming up to, then be warming up to 750 DEG C, soaking time 12h), obtain cobalt nickel oxide lithium aluminate material
Material；
3) after graphene oxide, is prepared using Hummers method, under the nitrogen atmosphere containing 5% hydrogen at 500 DEG C,
4h is restored, redox graphene is obtained；
4), by redox graphene ultrasonic disperse 2h in N-Methyl pyrrolidone obtained by step 3), then by step 2)
(the cobalt nickel oxide aluminium lithium material of the step 2) and the mass ratio of redox graphene are gained cobalt nickel oxide aluminium lithium material
99:1) it is added, after 50 DEG C of heating 8h, is dried in 80 DEG C of vacuum oven, redox graphene@cobalt nickel oxide is made
Aluminium lithium composite positive pole, wherein the chemical molecular formula of cobalt nickel oxide lithium material is LiNi0.815Co0.15Al0.035O2。
Embodiment 4
1), by nickel nitrate, cobalt nitrate and aluminum nitrate with molar ratio 0.815:0.15:0.035 is dissolved in deionized water and mixing
Uniformly, injection is full of in the continuous stirred tank reactor of argon gas, is then slowly dropped into sodium hydroxide and the control of ammonium hydroxide mixed alkali liquor is molten
Nickel cobalt lithium aluminate cathode material presoma is made with the progress of reaction in liquid pH value 11；
2), by cobalt lithium aluminate cathode material presoma and lithium hydroxide with 1:It is added after 1.05 molar ratio mixing appropriate
Dehydrated alcohol carries out ball milling 4h, drying；Taking-up is placed in high-temperature calcination stove 750 DEG C of calcining 12h (heating rates 5 under oxygen
DEG C/min, and 550 DEG C, soaking time 4h are warming up to, then be warming up to 750 DEG C, soaking time 12h), obtain cobalt nickel oxide lithium aluminate material
Material；
3) after graphene oxide, is prepared using Hummers method, under the nitrogen atmosphere containing 5% hydrogen at 500 DEG C,
4h is restored, redox graphene is obtained；
4), by redox graphene ultrasonic disperse 2h in N-Methyl pyrrolidone obtained by step 3), then by step 2)
(the cobalt nickel oxide aluminium lithium material of the step 2) and the mass ratio of redox graphene are gained cobalt nickel oxide aluminium lithium material
95:5) it is added, after 50 DEG C of heating 8h, is dried in 80 DEG C of vacuum oven, redox graphene@cobalt nickel oxide is made
Aluminium lithium composite positive pole, wherein the chemical molecular formula of cobalt nickel oxide aluminium lithium material is LiNi0.815Co0.15Al0.035O2。
As seen from the above embodiment, the present invention provides a kind of redox graphene-cobalt nickel oxide aluminium lithium anode composites
Material, the material with structure shown in formula I coated including redox graphene and the redox graphene：
LiNixCoyAl1-x-yO2Formula I；Wherein, 0.8<x<1,0.01<y<0.2.The composite positive pole by using inert matter also
Former graphene oxide cladding has the material of structure shown in formula I, and electric conductivity improves, thus make it have higher discharge capacity for the first time and
Cycle performance.Composite positive pole high rate performance also with higher and thermal stability.The experimental results showed that：2.7~
4.3V voltage, under 0.1C electric current, composite positive pole first discharge specific capacity reaches 215.8mAhg-1, for the first time coulombic efficiency be
91.01%；It is recycled 200 weeks under 1C electric current, capacity retention ratio is 85.6%；In 0.1C, 0.2C, 0.5C, 1C, 2C, 5C and 10C electricity
Under current density, the specific capacity of composite positive pole is respectively 215.8mAhg-1、190.4mAh·g-1、181.6mAh·g-1、
171.2mAh·g-1、160.1mAh·g-1、154.5mAh·g-1And 135.3mAhg-1；Redox graphene doping oxidation
Nickel cobalt aluminium lithium composite positive pole can effectively improve the absorption peak (264 DEG C of 256 DEG C of vs) of material, show the stabilization of material
Property is improved.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of redox graphene-cobalt nickel oxide aluminium lithium composite positive pole, including redox graphene and it is described also
The material with structure shown in formula I of former graphene oxide cladding：
LiNixCoyAl1-x-yO2Formula I；
Wherein, 0.8<x<1,0.01<y<0.2.
2. redox graphene according to claim 1-cobalt nickel oxide aluminium lithium combination electrode material, which is characterized in that
The mass ratio of the graphene and the material with structure shown in formula I is 0.5~5:95~99.5.
3. redox graphene according to claim 1-cobalt nickel oxide aluminium lithium combination electrode material, which is characterized in that
Described 0.8<x<0.85；0.12<y<0.2.
4. redox graphene according to claim 1-cobalt nickel oxide aluminium lithium combination electrode material, which is characterized in that
The x=0.815；Y=0.15.
5. a kind of preparation of any one of Claims 1 to 4 redox graphene-cobalt nickel oxide aluminium lithium composite positive pole
Method includes the following steps：
It is mixed after redox graphene is dispersed in a solvent with the material with structure shown in formula I, obtains redox graphene-
Cobalt nickel oxide aluminium lithium composite positive pole；
LiNixCoyAl1-x-yO2Formula I；
Wherein, 0.8<x<1,0.01<y<0.2.
6. preparation method according to claim 5, which is characterized in that the mixed temperature is 50~80 DEG C, mixing
Time is 2~8h.
7. preparation method according to claim 5, which is characterized in that the solvent be selected from N-Methyl pyrrolidone, acetone,
One of espeleton, methylisobutylketone, toluene and dimethylbenzene are a variety of.
8. preparation method according to claim 5, which is characterized in that the redox graphene is by following methods system
?：
After graphene oxide is prepared according to Hummers method, is restored in hydrogen and nitrogen mixture atmosphere, obtain reduction-oxidation
Graphene.
9. preparation method according to claim 5, which is characterized in that the material with structure shown in formula I is according to lower section
Method is made：
Nickel salt, cobalt salt, aluminium salt and water are mixed, adjust pH value to 10~13, reaction obtains nickel cobalt lithium aluminate cathode material forerunner
Body；
After the nickel cobalt lithium aluminate cathode material presoma and lithium salts are mixed, calcines, obtained with I knot of formula under oxygen atmosphere
The material of structure.
10. any one of a kind of lithium ion battery, including the Claims 1 to 4 redox graphene-cobalt nickel oxide aluminium lithium are multiple
Redox graphene-cobalt nickel oxide aluminium the lithium for closing the preparation method preparation of any one of positive electrode or claim 5~9 is multiple
Close positive electrode.
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