CN109873140A - A kind of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode and preparation method thereof - Google Patents
A kind of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrodes and preparation method thereof, the cobalt nickel oxide manganses lithium anode material that the positive electrode uses Template synthesis aluminium to adulterate first, then the cobalt nickel oxide manganses lithium anode material of aluminium doping and graphene are added in deionized water and are stirred evenly, hydro-thermal reaction is carried out, is centrifuged, washs and is dried to obtain cobalt nickel oxide manganses lithium anode material/grapheme composite positive electrode material of aluminium doping after cooling.The present invention passes through compound the advantages of can integrating two kinds of materials, improve electronic conductivity and ionic conductivity, the output power density for improving battery, but also can be improved the structural stability of ternary material, thus obtain cyclicity preferably, capacity is higher, the biggish composite positive pole of energy density.
Description
Technical field
The invention belongs to battery material technical field more particularly to a kind of silicon/carbon/graphite in lithium ion batteries alkene complex ternary anode materials
Material and preparation method thereof.
Background technique
Lithium ion battery is the secondary cell of new generation developed on the basis of lithium primary cell, is widely used in small portable
Electronic communication product and electric vehicle.The anode material for lithium-ion batteries of current industrialization mainly has cobalt acid lithium, changes
Property LiMn2O4, LiFePO4, ternary material etc..Although cobalt acid lithium performance is stablized, higher cost and cobalt element is toxic, Ke Nengzao
At environmental pollution.Lithium manganate having spinel structure is although cheap, but cause there are Jahn-Teller effect cycle performance compared with
Difference, and its chemical property is decayed because of the problems of dissolution of manganese comparatively fast at high temperature.LiFePO4 poorly conductive, product batch
Secondary disposable poor, poor performance at low temperatures, and there are problems that the dissolution of trace iron may cause battery short circuit.Therefore, the study found that
With LiNixCoyMn1-x-yO2For representative stratiform cobalt nickel oxide manganses series material (abbreviation ternary material) preferably had both it is above-mentioned
The advantages of material, and compensate its defect to a certain extent, there is height ratio capacity, stable cycle performance, advantage of lower cost, peace
The features such as full better performances, it is considered to be the ideal chose for mixed type electrical source of power.But simultaneously it there is also lower electricity
The disadvantages of conductance and capacity attenuation are fast, high rate performance is bad.
The preparation method of ternary material mainly has high temperature solid-state method, coprecipitation, sol-gel method, template etc. at present.
The present invention prepares the uniform cobalt nickel oxide manganses lithium material of particle using template, simplifies preparation process.The material of template preparation
Material can control the size of material, solve the problems, such as that conventional solid-state method granularity is uneven, material purity height, the grain prepared
Diameter is small, narrow distribution and sintering character is good.
Tertiary cathode material set LiNiO2、LiCoO2、LiMnO2Three kinds of positive electrode advantages, it is considered to be most have latent
One of widely applied positive electrode of power.The excellent performance of cobalt nickel oxide manganses lithium ternary material obtains domestic and international many research institutions
Concern, be not only widely used in small-sized electronic product, also there is preferable development trend on full-sized car power battery,
It has a good application prospect.But simultaneously it there is also lower conductivity and capacity attenuation it is fast, high rate performance is bad the disadvantages of,
In order to obtain more excellent tertiary cathode material, nickle cobalt lithium manganate is doped and is coated.Make lattice by ion doping
Certain distortion occurs, generates certain defect, improves electronic conductivity and ion diffusion rates, to improve high rate performance and follow
Ring performance.
Graphene is as two-dimentional carbon nanomaterial, due to the hexagon cellular shape void structure of its two-dimentional monolayer having
And excellent physico-chemical property, such as high specific surface area, high electronic conductivity, superior mechanical property and good chemical stabilization
Property etc., and it is widely used in lithium ion battery.In recent years many are research shows that graphene can be in composite positive pole
It forms conductive network and promotes its electric conductivity, while helping to shorten the diffusion path of lithium ion, fill the big multiplying power of positive electrode
Discharge performance has greatly improved, these are quite important for cobalt nickel oxide manganses lithium.
Summary of the invention
The present invention is directed to ternary layered positive electrode LiNixCol-x-y-zMnyAlzO2Poor repeatability and high rate performance, provide one
The silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode and its preparation side that kind technical process is simple, highly-safe, stability is good
Method.
The present invention is achieved by the following technical solutions:
A kind of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode, aluminium element is entered in cobalt nickel oxide manganses lithium lattice, is replaced
Co on portion3+, prepared after then mixing aluminium Y-oxides doping cobalt manganese lithium with graphene through hydro-thermal method.
The present invention also provides a kind of preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode, including it is following
Step:
(1) potassium permanganate is dissolved in certain deionized water, the concentrated hydrochloric acid of certain mol proportion is added dropwise thereto, stir 15 points
Clock is put into reaction kettle and carries out hydro-thermal reaction, is centrifuged after cooling, washs, be dried to obtain brown manganese dioxide, then in Muffle furnace
It is calcined 6 hours with 350 DEG C, obtains solid product A；
(2) solid product A obtained in step 1 and nickel source, cobalt source, silicon source and lithium salts are mixed to join by certain mol proportion
In the mixed solution of water and dehydrated alcohol, ultrasonic disperse 0.5-1 hours, then it is stirred and is evaporated, obtain solid mixture B,
B is ground, is then placed in crucible, after calcining, the cobalt nickel oxide manganses lithium LiNi of aluminium doping can be obtainedxCol-x-y-zMnyAlzO2
Positive electrode；
(3) LiNi for preparing graphene and step 2xCol-x-y-zMnyAlzO2Positive electrode is placed in water/ethylene glycol solution, dense
Degree is 0.01-0.02mol/L, ultrasonic disperse 0.5-2 hours, is then stirred, and is put into reaction kettle and carries out hydro-thermal reaction, cooling
Centrifuge washing obtains LiNi afterwardsxCol-x-y-zMnyAlzO2 / grapheme composite positive electrode material.
The temperature of hydro-thermal reaction is 140-160 DEG C in the step 1, and the reaction time is 8-14 hours, drying time 8-
12 hours, calcining heating rate was 2 DEG C/min.
Cobalt source is one or more of cobalt nitrate, cobalt acetate, cobalt chloride in the step 2；Nickel source is nickel nitrate, acetic acid
One or more of nickel, nickel chloride；Silicon source is one or more of aluminum nitrate, aluminium chloride；Lithium salts is lithium carbonate, acetic acid
One or more of lithium, lithium nitrate.
In the step 2 lithium salts, cobalt source, nickel source, silicon source and brown manganese dioxide according to certain mol proportion be dissolved in water and
In the mixed solution of dehydrated alcohol, holding concentration is 0.1-0.15mol/L.
The volume ratio of water and dehydrated alcohol is 1:0-10 in the mixed solution of water and dehydrated alcohol in the step 2.
For evaporated temperature at 60-75 DEG C, the calcination process is first to be warming up to 400-500 DEG C of calcining 5-8h in the step 2,
It is warming up to 750-850 DEG C of calcining 10-20h again, heating rate is 2 DEG C/min.
The cobalt nickel oxide manganses lithium LiNi of the doping of aluminium obtained in the step 2xCol-x-y-zMnyAlzO2Positive electrode, wherein 0
< x < 0.5,0 < y < 0.5,0 < z < 0.05.
The dosage of graphene accounts for LiNi in the step 3xCol-x-y-zMnyAlzO2The 1-10% of quality, the water and second two
The volume ratio of water and ethylene glycol is 1-2:1 in the mixed solution of alcohol.
The temperature of hydro-thermal reaction is 120-140 DEG C in the step 3, and the reaction time is 10-12 hours, drying temperature 70-
80 DEG C, the time is 8-12 hours.
The invention has the advantages that
1, composite positive pole of the present invention is the LiNi of a kind of more preferable cycle performance, more preferable high rate performancexCol-x-y-zMnyAlzO2/
Grapheme composite positive electrode material.
2, the invention is simple and feasible, and high production efficiency reduces production process, saves production cost and is not changed
The material of property is compared, and is greatly improved on battery capacity, high rate performance and cycle performance.
3, hydro-thermal method recombination energy improves LiNixCol-x-y-zMnyAlzO2Adhesive force between graphene, makes
LiNixCol-x-y-zMnyAlzO2It is dispersed in one conductive network of formation between graphene sheet layer, so as to improve lithium ion
The cycle performance and high rate performance of battery.
Detailed description of the invention
Fig. 1 show LiNi1/3Co1/3Mn1/3O2And LiNi1/3Co1/3-0.03Mn1/3Al0.03O2XRD spectrum.
Fig. 2 show LiNi1/3Co1/3-0.05Mn1/3Al0.05O2And LiNi1/3Co1/3-0.05Mn1/3Al0.05O2/ graphene
Raman map.
Fig. 3 show LiNi1/3Co1/3Mn1/3O2、LiNi1/3Co1/3-0.05Mn1/3Al0.05O2And LiNi1/3Co1/3-0.05Mn1/ 3Al0.05O2/ graphene first charge-discharge curve at 0.1C.
Fig. 4 show LiNi1/3Co1/3-0.05Mn1/3Al0.05O2And LiNi1/3Co1/3-0.05Mn1/3Al0.05O2/ graphene is compound
The cycle performance figure of positive electrode.
Fig. 5 show the LiNi of the preparation of embodiment 41/3Co1/3-0.05Mn1/3Al0.05O2/ grapheme composite positive electrode material
SEM figure.
Specific embodiment
Below in conjunction with specific example, technical scheme is described further:
Embodiment 1
The preparation method of lithium ion battery cobalt nickel oxide manganses lithium anode material in the present embodiment, comprising the following steps:
(1) it weighs 0.79g potassium permanganate to be dissolved in 50ml deionized water, stirring makes it completely dissolved for 15 minutes, then thereto
The hydrochloric acid of 2ml 37% is added dropwise, continues stirring 15 minutes, is then transferred in reaction kettle, is reacted 12 hours at 140 DEG C, is centrifuged, washes
It washs, is 12 hours dry at 70 DEG C, products therefrom is transferred to crucible, is calcined 6 hours in Muffle furnace with 350 DEG C, obtains institute
Need MnO2；
(2) 0.5481g lithium nitrate, 0.2174g manganese dioxide, nine nitric hydrate cobalt of 0.7276g are weighed, 0.7270g nine is hydrated nitre
Sour nickel is dissolved in the mixed solution of 50ml water and 50ml ethyl alcohol, in order to make up the loss of lithium source in calcination process, lithium nitrate mistake
Amount 6%；Ultrasound 1 hour continues stirring 6 hours, then continues stirring at 70 DEG C and is evaporated, will be put into earthenware after the solid abrasive being evaporated
It in crucible, is placed in Muffle furnace, is warming up to 480 DEG C in air atmosphere with the heating rate of 2 DEG C/min, 5h is calcined, followed by of continuing rising
Temperature calcines 16h to 850 DEG C, then cools to room temperature with the furnace, takes out sample and regrinds to obtain LiNi1/3Co1/3Mn1/3O2Powder
End；
By LiNi obtained1/3Co1/3Mn1/3O2It is mixed with acetylene black and Kynoar (PVDF) by the mass ratio of 8:1:1
It is even, it is rolled into thick 120 μm of film, the anode after 120 DEG C of vacuum drying 10h, as experiment half-cell；Using 1mol/L
LiPF6/ ethylene carbonate (EC)-dimethyl carbonate (DMC) (the volume ratio 1:1 of EC and DMC) electrolyte, fills in dry
In the glove box of full argon gas, using metal lithium sheet as cathode, it is assembled into battery.With LiNi prepared by the present embodiment1/3Co1/ 3Mn1/3O2For anode, using lithium piece as the button cell of cathode, in 2.5-4.3V voltage range, with constant current-constant pressure under 0.1C multiplying power
It charges, first discharge specific capacity is 175mAh/g when constant-current discharge under 0.1C multiplying power, but capacity is only after 30 circulations
157mAh/g。
Embodiment 2
The preparation method of lithium ion battery aluminium Y-oxides doping cobalt manganese lithium anode material in the present embodiment, comprising the following steps:
(1) it weighs 0.79g potassium permanganate to be dissolved in 50ml deionized water, stirring makes it completely dissolved for 15 minutes, then thereto
The hydrochloric acid of 2ml 37% is added dropwise, continues stirring 15 minutes, is then transferred in reaction kettle, is reacted 12 hours at 140 DEG C, is centrifuged, washes
It washs, is 12 hours dry at 70 DEG C, products therefrom is transferred to crucible, is calcined 6 hours in Muffle furnace with 350 DEG C, obtains institute
Need MnO2；
(2) 0.5481g lithium nitrate, 0.2174g manganese dioxide, nine nitric hydrate cobalt of 0.6620g are weighed, 0.7270g nine is hydrated nitre
Sour nickel, 0.0844g ANN aluminium nitrate nonahydrate are dissolved in the mixed solution of 50ml water and 50ml ethyl alcohol, in order to make up in calcination process
The loss of lithium source, lithium nitrate excessive 6%；Ultrasound 1 hour continues stirring 6 hours, then continues stirring at 70 DEG C and is evaporated, will be evaporated
Solid abrasive after be put into crucible, be placed in Muffle furnace, be warming up to 480 in air atmosphere with the heating rate of 2 DEG C/min
DEG C, 5h is calcined, it is further heated up to 850 DEG C, 16h is calcined, then cools to room temperature with the furnace, sample is taken out and regrinds to obtain
LiNi1/3Co1/3-0.03Mn1/3Al0.03O2Powder.
The LiNi that experiment is prepared1/3Co1/3Mn1/3O2And LiNi1/3Co1/3-0.03Mn1/3Al0.03O2X-ray diffraction
Spectrogram is shown in Fig. 1.From figure 1 it appears that the LiNi of preparation1/3Co1/3-0.05Mn1/3Al0.05O2Positive electrode with it is undoped
LiNi1/3Co1/3Mn1/3O2The XRD diagram peak shape of material is identical, miscellaneous peak does not occur, this may be that Al enters LiNi1/3Co1/3Mn1/ 3O2In lattice, replace the Co on portion3+, this illustrates that doping has no effect on main body layer structure.
By LiNi obtained1/3Co1/3-0.03Mn1/3Al0.03O2With acetylene black and Kynoar (PVDF) by 8:1:1's
Mass ratio is uniformly mixed, and is rolled into thick 120 μm of film, the anode after 120 DEG C of vacuum drying 10h, as experiment half-cell；It adopts
With 1mol/L LiPF6/ ethylene carbonate (EC)-dimethyl carbonate (DMC) (the volume ratio 1:1 of EC and DMC) electrolyte,
In the dry glove box full of argon gas, using metal lithium sheet as cathode, it is assembled into battery.Prepared by the present embodiment
LiNi1/3Co1/3-0.03Mn1/3Al0.03O2For anode, using lithium piece as the button cell of cathode, in 2.5-4.3V voltage range, with
Constant current-constant-voltage charge under 0.1C multiplying power, first discharge specific capacity is 186mAh/g when constant-current discharge under 0.1C multiplying power, but passes through 30
Capacity is 175mAh/g after secondary circulation.
Embodiment 3
The preparation method of lithium ion battery aluminium Y-oxides doping cobalt manganese lithium anode material in the present embodiment, comprising the following steps:
(1) it weighs 0.79g potassium permanganate to be dissolved in 50ml deionized water, stirring makes it completely dissolved for 15 minutes, then thereto
The hydrochloric acid of 2ml 37% is added dropwise, continues stirring 15 minutes, is then transferred in reaction kettle, is reacted 12 hours at 140 DEG C, is centrifuged, washes
It washs, is 12 hours dry at 70 DEG C, products therefrom is transferred to crucible, is calcined 6 hours in Muffle furnace with 350 DEG C, obtains institute
Need MnO2；
(2) 0.5481g lithium nitrate, 0.2174g manganese dioxide, nine nitric hydrate cobalt of 0.6183g are weighed, 0.7270g nine is hydrated nitre
Sour nickel, 0.1406g ANN aluminium nitrate nonahydrate are dissolved in the mixed solution of 50ml water and 50ml ethyl alcohol, in order to make up in calcination process
The loss of lithium source, lithium nitrate excessive 6%；Ultrasound 1 hour continues stirring 6 hours, then continues stirring at 70 DEG C and is evaporated, will be evaporated
Solid abrasive after be put into crucible, be placed in Muffle furnace, be warming up to 480 in air atmosphere with the heating rate of 2 DEG C/min
DEG C, 5h is calcined, it is further heated up to 850 DEG C, 16h is calcined, then cools to room temperature with the furnace, sample is taken out and regrinds to obtain
LiNi1/3Co1/3-0.05Mn1/3Al0.05O2Powder.
By LiNi obtained1/3Co1/3-0.05Mn1/3Al0.05O2With acetylene black and Kynoar (PVDF) by 8:1:1's
Mass ratio is uniformly mixed, and is rolled into thick 120 μm of film, the anode after 120 DEG C of vacuum drying 10h, as experiment half-cell；It adopts
With 1mol/L LiPF6/ ethylene carbonate (EC)-dimethyl carbonate (DMC) (the volume ratio 1:1 of EC and DMC) electrolyte,
In the dry glove box full of argon gas, using metal lithium sheet as cathode, it is assembled into battery.Prepared by the present embodiment
LiNi1/3Co1/3-0.05Mn1/3Al0.05O2For anode, using lithium piece as the button cell of cathode, in 2.5-4.3V voltage range, with
Constant current-constant-voltage charge under 0.1C multiplying power, first discharge specific capacity is 186mAh/g when constant-current discharge under 0.2C multiplying power, but passes through 30
Capacity is only 178mAh/g after secondary circulation.
Embodiment 4
Lithium ion battery aluminium Y-oxides doping cobalt manganese lithium/graphene anode material preparation method in the present embodiment, including with
Lower step:
(1) it weighs 0.79g potassium permanganate to be dissolved in 50ml deionized water, stirring makes it completely dissolved for 15 minutes, then thereto
The hydrochloric acid of 2ml 37% is added dropwise, continues stirring 15 minutes, is then transferred in reaction kettle, is reacted 12 hours at 140 DEG C, is centrifuged, washes
It washs, is 12 hours dry at 70 DEG C, products therefrom is transferred to crucible, is calcined 6 hours in Muffle furnace with 350 DEG C, obtains institute
Need MnO2；
(2) 0.5481g lithium nitrate, 0.2174g manganese dioxide, nine nitric hydrate cobalt of 0.6183g are weighed, 0.7270g nine is hydrated nitre
Sour nickel, 0.1406g ANN aluminium nitrate nonahydrate are dissolved in the mixed solution of 50ml water and 50ml ethyl alcohol, in order to make up in calcination process
The loss of lithium source, lithium nitrate excessive 6%；Ultrasound 1 hour continues stirring 6 hours, then continues stirring at 70 DEG C and is evaporated, will be evaporated
Solid abrasive after be put into crucible, be placed in Muffle furnace, be warming up to 480 in air atmosphere with the heating rate of 2 DEG C/min
DEG C, 5h is calcined, it is further heated up to 850 DEG C, 16h is calcined, then cools to room temperature with the furnace, sample is taken out and regrinds to obtain
LiNi1/3Co1/3-0.05Mn1/3Al0.05O2Powder；
(3) resulting LiNi is weighed1/3Co1/3-0.05Mn1/3Al0.05O2Powder 0.3g, graphene 0.009g be dispersed in 30ml go from
It in the mixed solution of sub- water and 20ml ethylene glycol, ultrasonic disperse 1 hour, goes on blender and stirs 6 hours, be then transferred into anti-
It answers in kettle and is reacted 8 hours at 120 DEG C, be centrifuged after cooling, washing, drying 12 hours at 70 DEG C, obtain LiNi1/3Co1/3- 0.05Mn1/3Al0.05O2/ GR-3wt% material.
The LiNi that embodiment is prepared1/3Co1/3-0.05Mn1/3Al0.05O2And LiNi1/3Co1/3-0.05Mn1/3Al0.05O2/
The Raman spectrogram of GR-3wt% is shown in Fig. 2.From figure 2 it can be seen that the LiNi of preparation1/3Co1/3-0.05Mn1/3Al0.05O anode material
Expect graphene peak do not occur, but the LiNi of composite graphite alkene1/3Co1/3-0.05Mn1/3Al0.05O2/ GR-3wt% material
There is graphene peak in Raman figure, this may be that graphene is compounded in LiNi1/3Co1/3-0.05Mn1/3Al0.05The table of O positive electrode
Face.
By LiNi obtained1/3Co1/3-0.05Mn1/3Al0.05O2/ GR-3wt% is pressed with acetylene black and Kynoar (PVDF)
The mass ratio of 8:1:1 is uniformly mixed, and is rolled into thick 120 μm of film, after 120 DEG C of vacuum drying 10h, as experiment half-cell
Anode；Using 1mol/L LiPF6/ethylene carbonate (EC)-dimethyl carbonate (DMC) (the volume ratio 1:1 of EC and DMC)
Electrolyte using metal lithium sheet as cathode, is assembled into battery in the dry glove box full of argon gas.With the present embodiment institute
The LiNi of preparation1/3Co1/3-0.05Mn1/3Al0.05O2/ GR-3wt% is anode, using lithium piece as the button cell of cathode, in 2.5-
4.3V voltage range, with constant current-constant-voltage charge under 0.1C multiplying power, first discharge specific capacity is when constant-current discharge under 0.1C multiplying power
163mAh/g, but capacity is only 158mAh/g after 30 circulations.
Claims (10)
1. a kind of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode, which is characterized in that aluminium element is entered cobalt nickel oxide manganses
In lithium lattice, replace the Co on portion3+, through hydro-thermal legal system after then aluminium Y-oxides doping cobalt manganese lithium is mixed with graphene
It is standby to obtain.
2. a kind of preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode, which comprises the following steps:
(1) potassium permanganate is dissolved in certain deionized water, the concentrated hydrochloric acid of certain mol proportion is added dropwise thereto, stir 15 points
Clock is put into reaction kettle and carries out hydro-thermal reaction, is centrifuged after cooling, washs, be dried to obtain brown manganese dioxide, then in Muffle furnace
It is calcined 6 hours with 350 DEG C, obtains solid product A；
(2) solid product A obtained in step 1 and nickel source, cobalt source, silicon source and lithium salts are mixed to join by certain mol proportion
In the mixed solution of water and dehydrated alcohol, ultrasonic disperse 0.5-1 hours, then it is stirred and is evaporated, obtain solid mixture B,
B is ground, is then placed in crucible, after calcining, the cobalt nickel oxide manganses lithium LiNi of aluminium doping can be obtainedxCol-x-y-zMnyAlzO2
Positive electrode；
(3) LiNi for preparing graphene and step 2xCol-x-y-zMnyAlzO2Positive electrode is placed in water/ethylene glycol solution, dense
Degree is 0.01-0.02mol/L, ultrasonic disperse 0.5-2 hours, is then stirred, and is put into reaction kettle and carries out hydro-thermal reaction, cooling
Centrifuge washing obtains LiNi afterwardsxCol-x-y-zMnyAlzO2 / grapheme composite positive electrode material.
3. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In the temperature of hydro-thermal reaction is 140-160 DEG C in the step 1, and the reaction time is 8-14 hours, and drying time is that 8-12 is small
When, calcining heating rate is 2 DEG C/min.
4. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In cobalt source is one or more of cobalt nitrate, cobalt acetate, cobalt chloride in the step 2；Nickel source is nickel nitrate, nickel acetate, chlorine
Change one or more of nickel；Silicon source is one or more of aluminum nitrate, aluminium chloride；Lithium salts is lithium carbonate, lithium acetate, nitric acid
One or more of lithium.
5. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In lithium salts, cobalt source, nickel source, silicon source and brown manganese dioxide are dissolved in water and anhydrous second according to certain mol proportion in the step 2
In the mixed solution of alcohol, holding concentration is 0.1-0.15mol/L.
6. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In the volume ratio of water and dehydrated alcohol is 1:0-10 in the mixed solution of water and dehydrated alcohol in the step 2.
7. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In for evaporated temperature at 60-75 DEG C, the calcination process is first to be warming up to 400-500 DEG C of calcining 5-8h, then rise in the step 2
For temperature to 750-850 DEG C of calcining 10-20h, heating rate is 2 DEG C/min.
8. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In the cobalt nickel oxide manganses lithium LiNi of the doping of aluminium obtained in the step 2xCol-x-y-zMnyAlzO2Positive electrode, wherein 0 < x <
0.5,0 < y < 0.5,0 < z < 0.05.
9. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In the dosage of graphene accounts for LiNi in the step 3xCol-x-y-zMnyAlzO2The 1-10% of quality, the water and ethylene glycol
The volume ratio of water and ethylene glycol is 1-2:1 in mixed solution.
10. the preparation method of silicon/carbon/graphite in lithium ion batteries alkene complex ternary positive electrode according to claim 2, feature exist
In, in the step 3 temperature of hydro-thermal reaction be 120-140 DEG C, the reaction time be 10-12 hours, 70-80 DEG C of drying temperature,
Time is 8-12 hours.
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| CN111530470A (en) * | 2020-05-06 | 2020-08-14 | 合肥工业大学 | Preparation method of manganese dioxide and composite material thereof and degradation method of sulfadiazine |
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