CN109768233A - Lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole - Google Patents
Lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole Download PDFInfo
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- CN109768233A CN109768233A CN201811518515.5A CN201811518515A CN109768233A CN 109768233 A CN109768233 A CN 109768233A CN 201811518515 A CN201811518515 A CN 201811518515A CN 109768233 A CN109768233 A CN 109768233A
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Abstract
The invention discloses lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole, comprising the following steps: (1) successively pre-process resin；(2) resin is added in catalyst metal salt solution, which is the mixture of nickel salt solution and cobalt salt solution, stirring, drying, crushing；(3) pore creating material is added, stirs evenly, dries；(4) under the protection of inert atmosphere, 500-900 DEG C of high-temperature process 1-3h is cooled to room temperature, washing, filtering, drying；(5) it is configured to mixed solution with sulfur-containing compound, carries out hydro-thermal reaction, temperature is 160-200 DEG C, time 12-24h, and filtering washes, is dry；(6) under the protection of inert atmosphere, 500-700 DEG C of high-temperature process 1-3h is cooling to get lithium ion battery NiCo2S4/ graphene composite negative pole.The method of the present invention prepares cell negative electrode material, good conductivity, large specific surface area, and cyclical stability is fabulous.
Description
Technical field
The present invention relates to lithium cell cathode material technical field, in particular to a kind of lithium ion battery NiCo2S4/ graphene
The preparation method of composite negative pole material.
Background technique
In recent years, environmental pollution and energy shortage problem are got worse, there is an urgent need to develop efficient, green and environmental protection it is new
The energy, and wherein high, charge and discharge energy densities are high, matter is small and light, power density is high, uses the longevity with voltage for lithium ion battery
Advantage of waiting so long is ordered, the energy storage devices such as portable electronic device, electric car are widely used in.Lithium ion battery uses field
It is continuous expand and people are to the swift and violent demand of portable electronic product, pushed high power density, high-energy density, long used
Service life, cheap and environmental-friendly new type lithium ion electrode material continuous research and development.
However the problems such as commercial graphite cathode material is low there is specific capacity at this stage, design and prepare the electricity haveing excellent performance
The feasible scheme of pole material is extremely urgent.Transient metal sulfide because its is from a wealth of sources and have active site abundant,
It can be used as diversified electrode material, and receive significant attention.But transient metal sulfide poorly conductive, volume expansion are tight
It is poor that the problems such as weight, results in its cycle performance.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
The purpose of the present invention is to provide a kind of lithium ion battery NiCo2S4The preparation side of/graphene composite negative pole
Method, transient metal sulfide is easy to reunite, easily reacts and decomposes with electrolyte to solve, and lithium ion battery negative material is caused to exist
The problems such as energy density is not high and cycle performance is undesirable.
To achieve the above object, the present invention provides a kind of lithium ion battery NiCo2S4/ graphene composite negative pole
Preparation method, comprising the following steps:
(1) resin successively pre-processed, cleaned, dried；
(2) the gained resin of step (1) after dry is added in catalyst metal salt solution, which is nickel
The mixture of salting liquid and cobalt salt solution, stirring, drying crush；
(3) pore creating material is added in obtained material after crushing in step (2), stirs evenly, and dries；
(4) obtained material is under the protection of inert atmosphere after crushing step (3), and 500-900 DEG C of high-temperature process 1-3h is cold
But to room temperature, washing, filtering, drying；
(5) obtained material after drying in step (4) and sulfur-containing compound are configured to mixed solution, are transferred to reaction kettle progress
Hydro-thermal reaction, temperature are 160-200 DEG C, time 12-24h, filtering, washing, drying；
(6) obtained material is under the protection of inert atmosphere after will be dry in step (5), 500-700 DEG C of high-temperature process 1-3h,
It is cooled to room temperature to get lithium ion battery NiCo2S4/ graphene composite negative pole.
Preferably, in above-mentioned technical proposal, resin described in step (1) is ion exchange resin, chelating resin, epoxy
The mixture of one or more of resin, phenolic resin.
Preferably, in above-mentioned technical proposal, pretreatment described in step (1) is followed successively by alkali process and acid processing.
Preferably, in above-mentioned technical proposal, catalyst metals salinity is 0.05-0.2mol/L in step (2), described
Catalyst metal salts are nickel salt, two kinds of mixtures in cobalt salt, and the molar ratio of nickel salt and cobalt salt mixing is 1:1-1:5；Wherein, described
Nickel salt be nickel acetate tetrahydrate, Nickel dichloride hexahydrate, Nickelous nitrate hexahydrate or six hydration nickel sulfate；The cobalt salt is four water
Close cobalt acetate, cobalt chloride hexahydrate, cabaltous nitrate hexahydrate or Cobalt monosulfate heptahydrate.
Preferably, in above-mentioned technical proposal, the mass ratio of obtained material and pore creating material is 1:1-1:5 in step (3), described
Pore creating material be one or more of potassium hydroxide, saleratus, sodium hydroxide, sodium bicarbonate mixture.
Preferably, in above-mentioned technical proposal, inert atmosphere described in step (4) is in argon gas, nitrogen, hydrogen or helium
One or more kinds of mixtures, inert atmosphere flow control is in 30~100cc/min.
Preferably, in above-mentioned technical proposal, high-temperature process described in step (4) is in tube furnace or atmosphere Muffle furnace
It carries out, the heating rate before high-temperature process is 1-10 DEG C/min.
Preferably, in above-mentioned technical proposal, sulfur-containing compound described in step (5) is thiocarbamide, L-methionine, half Guang
The mixture of one or more of propylhomoserin, cystine.
Preferably, obtained material and sulfur-containing compound after step (4) are dried are added in above-mentioned technical proposal, in step (5)
Mass ratio be 1:1-1:5.
Preferably, in above-mentioned technical proposal, inert atmosphere described in step (6) is in argon gas, nitrogen, hydrogen or helium
One or more kinds of mixtures.
Lithium ion battery NiCo of the present invention2S4The reaction principle of the preparation method of/graphene composite negative pole is as follows:
Graphene has excellent electric conductivity, high electron mobility, big specific surface area, can effectively inhibit volume swollen
Integrality that is swollen and keeping structure.Transient metal sulfide is because its is from a wealth of sources and has active site abundant, Ke Yizuo
For diversified electrode material.The two is combined and is prepared into composite material, realizes being obviously improved for material property.Nickel, cobalt
In base sulfide, ternary negative electrode material is capable of providing richer chemical reaction, improves the chemical property of material.This nickel member
Synergistic effect between element and cobalt element is capable of the electric conductivity of reinforcing material, is capable of providing a buffer layer and improves constantly
The volume expansion occurred in charge and discharge process.Cobalt element can provide a very high theoretical capacity for material, and nickel element with
Other metal hybrids, while reinforcement material electric conductivity, the transport property of lithium ion and electronics can also be improved.Pass through introducing
The graphene of high-specific surface area inhibits NiCo2S4Volume expansion in charge and discharge process, and the good electric conductivity of graphene solves
NiCo2S4The decaying of capacity in charge and discharge process, to prepare the lithium ion battery for having both high power density and high-energy density
Negative electrode material.
Compared with prior art, the invention has the following beneficial effects:
(1) lithium ion battery NiCo of the present invention2S4The preparation method of/graphene composite negative pole, by utilizing resin energy
Effectively, the metal ion with catalytic action is uniformly exchanged, so that metal ion is distributed evenly in resin, localization catalysis
Graphitization forms graphene layer.By adding pore creating material, pore-creating is carried out to carbon material, by changing the dosage of pore creating material, thus
The pattern for regulating and controlling final product obtains different specific surface areas, the graphene powder of the three-dimensional multistage pore structure of different pore size distribution.
NiCo2S4The electric conductivity that material is improved with graphene In-situ reaction is conducive to the transmission of electronics, while the graphite of porous structure
Alkene inhibition restrained effectively NiCo2S4Reunite and alleviate the volume change in cyclic process, improves the stable circulation of material
Property and lithium storage content.Raw material is low in cost in the present invention, and synthesis process is easily controllable, it is easy to accomplish industrial mass production,
Help to push application of the transient metal sulfide in terms of lithium ion battery negative material.
(2) lithium ion battery NiCo is prepared for using high-temperature sintering process and hydro-thermal method in the method for the present invention2S4/ graphene is multiple
Negative electrode material is closed, does not need that template is added and introduces carbon material to make substrate, directlys adopt the resin for having exchanged nickel and cobalt element
Presoma Ni-Co/ graphene is synthesized by the method for high temperature sintering, this presoma is formed in situ with thiocarbamide hydro-thermal reaction again
NiCo2S4/ graphene.The negative electrode material has great specific surface area, shortens insertion/deintercalation of electron-transport and lithium ion
Path, while alleviating NiCo in charge and discharge process2S4The volume expansion of nano particle；Due to the collaboration between nickel and cobalt element
Effect improves the reversible capacity and cyclical stability of lithium ion battery, therefore NiCo2S4/ graphene is a kind of ideal cathode material
Material.
(3) the method for the present invention low production cost, synthesis process is easily controllable, and yield height is, it can be achieved that large scale preparation；System
Standby resulting NiCo2S4When/graphene combination electrode material is used as negative electrode of lithium ion battery, good conductivity, large specific surface area is followed
Ring excellent stability has potential application prospect in the fields such as portable electronic device and hybrid-electric car.
Detailed description of the invention
Fig. 1 is the preparation gained lithium ion battery of embodiment according to the present invention 1 NiCo2S4/ graphene composite negative pole is micro-
See topography scan Electronic Speculum phenogram.
Fig. 2 is the preparation gained lithium ion battery of embodiment according to the present invention 1 NiCo2S4/ graphene composite negative pole is micro-
See pattern transmission electron microscope phenogram.
Fig. 3 is the preparation gained lithium ion battery of embodiment according to the present invention 1 NiCo2S4/ graphene composite negative pole
X-ray diffraction analysis figure.
Fig. 4 is the preparation gained lithium ion battery of embodiment according to the present invention 1 NiCo2S4/ graphene composite negative pole
Nitrogen adsorption desorption curve and graph of pore diameter distribution.
Fig. 5 is the preparation gained lithium ion battery of embodiment according to the present invention 1 NiCo2S4/ graphene composite negative pole
Chemical property figure.
Specific embodiment
With reference to the accompanying drawing, specific embodiments of the present invention will be described in detail, it is to be understood that guarantor of the invention
Shield range is not limited by the specific implementation.
Unless otherwise explicitly stated, otherwise in entire disclosure and claims, term " includes " or its change
Changing such as "comprising" or " including " etc. will be understood to comprise stated element or component, and not exclude other members
Part or other component parts.
Embodiment 1
A kind of lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole, operating procedure are as follows:
(1) ion exchange resin is successively carried out to alkali process and acid processing, cleaning, drying；
(2) will it is dry in step (1) after gained ion exchange resin be added to 0.1mol/L nickel acetate tetrahydrate and
In the mixed solution of tetra- acetate hydrate cobalt of 0.2mol/L, after stirring 12h, solution is removed, drying crushes；
(3) potassium hydroxide pore creating material is added in obtained material 1:1 in mass ratio after crushing in step (2), stirs evenly, and dries
It is dry；
(4) obtained material after drying in step (3) is put into tube furnace, in the protection that argon flow is 40cc/min
Under, 550 DEG C are risen to from room temperature with 5 DEG C/min of heating rate, then rise to 850 DEG C and high-temperature process 2h with 2 DEG C/min, is cooled to room
Temperature washes 12h, filtering, drying；
(5) in mass ratio it is that 1:1 is configured to mixed solution by obtained material after drying in step (4) and thiocarbamide, is transferred to anti-
Kettle is answered to carry out hydro-thermal reaction, temperature is 200 DEG C, and the time is that for 24 hours, filtering washes, is dry；
(6) obtained material is put into tube furnace after will be dry in step (5), in the protection that argon flow is 40cc/min
Under, 500 DEG C and high-temperature process 2h are risen to from room temperature with 5 DEG C/min of heating rate, is cooled to room temperature to get lithium ion battery
NiCo2S4/ graphene composite negative pole.
The composite negative pole material that the present embodiment is prepared is detected
As depicted in figs. 1 and 2, Fig. 1 is that the present embodiment prepares gained lithium ion battery NiCo2S4/ graphene composite negative material
Expect that microscopic appearance scanning electron microscope phenogram, Fig. 2 are that the present embodiment prepares gained lithium ion battery NiCo2S4/ graphene composite negative
Material microscopic appearance transmission electron microscope phenogram.Graphene is presented three-dimensional porous pleated structure and mentions for material as we can see from the figure
Supplied big specific surface area, and graphene coated NiCo2S4 nano particle, it is suppressed that it is reunited.
As shown in figure 3, Fig. 3 is the present embodiment preparation gained lithium ion battery NiCo2S4The X of/graphene composite negative pole
X ray diffraction analysis x figure, NiCo2S4With JCPDS No.20-0782 standard card NiCo2S4Peak it is consistent, and high-visible stone
The hump of black alkene (002) crystal face.
Fig. 4 is the present embodiment preparation gained lithium ion battery NiCo2S4The nitrogen adsorption desorption of/graphene composite negative pole
Curve and graph of pore diameter distribution, BET specific surface area is 1036.5m in Fig. 4 a2/g；In Fig. 4 b known to the combination electrode material mainly by
Micropore composition, in addition there are some mesoporous and macropores.
Fig. 5 is the present embodiment preparation gained lithium ion battery NiCo2S4The chemical property of/graphene composite negative pole
Figure, from can be seen that in the cycle performance figure of Fig. 5 a under the high current density of 2000mA/g by the charge and discharge of 500 circulations
Afterwards, the discharge capacity of this combination electrode material still maintains as 481.6mAh/g.It can be seen that from the high rate performance figure of Fig. 5 b
Under the low current density of 200mA/g, the discharge capacity of this combination electrode material is 755.4mAh/g；As a result illustrate: lithium ion
Battery NiCo2S4/ graphene composite negative pole shows fabulous cyclical stability and outstanding high rate performance.
Embodiment 2
A kind of lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole, operating procedure are as follows:
(1) ion exchange resin is successively carried out to alkali process and acid processing, cleaning, drying；
(2) will it is dry in step (1) after gained ion exchange resin be added to 0.1mol/L nickel acetate tetrahydrate and
In the mixed solution of 0.1mol/L cobalt chloride hexahydrate, after stirring 12h, solution is removed, drying crushes；
(3) potassium hydroxide pore creating material is added in obtained material 1:2 in mass ratio after crushing in step (2), stirs evenly, and dries
It is dry；
(4) obtained material after drying in step (3) is put into tube furnace, in the protection that argon flow is 40cc/min
Under, 550 DEG C are risen to from room temperature with 5 DEG C/min of heating rate, then rise to 850 DEG C and high-temperature process 2h with 2 DEG C/min, is cooled to room
Temperature washes 12h, filtering, drying；
(5) in mass ratio it is that 1:2 is configured to mixed solution by obtained material after drying in step (4) and thiocarbamide, is transferred to anti-
Kettle is answered to carry out hydro-thermal reaction, temperature is 200 DEG C, and the time is that for 24 hours, filtering washes, is dry；
(6) obtained material is put into tube furnace after will be dry in step (5), in the protection that argon flow is 40cc/min
Under, 500 DEG C and high-temperature process 2h are risen to from room temperature with 5 DEG C/min of heating rate, is cooled to room temperature to get lithium ion battery
NiCo2S4/ graphene composite negative pole.
Embodiment 3
A kind of lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole, operating procedure are as follows:
(1) ion exchange resin is successively carried out to alkali process and acid processing, cleaning, drying；
(2) will it is dry in step (1) after gained ion exchange resin be added to 0.1mol/L nickel acetate tetrahydrate and
In the mixed solution of 0.3mol/L cobalt chloride hexahydrate, after stirring 12h, solution is removed, drying crushes；
(3) saleratus pore creating material is added in obtained material 1:3 in mass ratio after crushing in step (2), stirs evenly, and dries
It is dry；
(4) obtained material after drying in step (3) is put into tube furnace, in the protection that argon flow is 40cc/min
Under, 550 DEG C are risen to from room temperature with 5 DEG C/min of heating rate, then rise to 850 DEG C and high-temperature process 2h with 2 DEG C/min, is cooled to room
Temperature washes 12h, filtering, drying；
(5) in mass ratio it is that 1:3 is configured to mixed solution by obtained material after drying in step (4) and thiocarbamide, is transferred to anti-
Kettle is answered to carry out hydro-thermal reaction, temperature is 180 DEG C, and the time is that for 24 hours, filtering washes, is dry；
(6) obtained material is put into tube furnace after will be dry in step (5), in the protection that argon flow is 40cc/min
Under, 500 DEG C and high-temperature process 2h are risen to from room temperature with 5 DEG C/min of heating rate, is cooled to room temperature to get lithium ion battery
NiCo2S4/ graphene composite negative pole.
Embodiment 4
A kind of lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole, operating procedure are as follows:
(1) ion exchange resin is successively carried out to alkali process and acid processing, cleaning, drying；
(2) will it is dry in step (1) after gained ion exchange resin be added to 0.1mol/L nickel acetate tetrahydrate and
In the mixed solution of tetra- acetate hydrate cobalt of 0.4mol/L, after stirring 12h, solution is removed, drying crushes；
(3) saleratus pore creating material is added in obtained material 1:4 in mass ratio after crushing in step (2), stirs evenly, and dries
It is dry；
(4) obtained material after drying in step (3) is put into tube furnace, in the protection that argon flow is 40cc/min
Under, 550 DEG C are risen to from room temperature with 5 DEG C/min of heating rate, then rise to 850 DEG C and high-temperature process 2h with 2 DEG C/min, is cooled to room
Temperature washes 12h, filtering, drying；
(5) in mass ratio it is that 1:4 is configured to mixed solution by obtained material after drying in step (4) and thiocarbamide, is transferred to anti-
Kettle is answered to carry out hydro-thermal reaction, temperature is 200 DEG C, and the time is that for 24 hours, filtering washes, is dry；
(6) obtained material is put into tube furnace after will be dry in step (5), in the protection that argon flow is 40cc/min
Under, 500 DEG C and high-temperature process 2h are risen to from room temperature with 5 DEG C/min of heating rate, is cooled to room temperature to get lithium ion battery
NiCo2S4/ graphene composite negative pole.
Embodiment 5
A kind of lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole, operating procedure are as follows:
(1) ion exchange resin is successively carried out to alkali process and acid processing, cleaning, drying；
(2) will it is dry in step (1) after gained ion exchange resin be added to 0.1mol/L nickel acetate tetrahydrate and
In the mixed solution of 0.5mol/L cobalt chloride hexahydrate, after stirring 12h, solution is removed, drying crushes；
(3) potassium hydroxide pore creating material is added in obtained material 1:5 in mass ratio after crushing in step (2), stirs evenly, and dries
It is dry；
(4) obtained material after drying in step (3) is put into tube furnace, in the protection that argon flow is 40cc/min
Under, 550 DEG C are risen to from room temperature with 5 DEG C/min of heating rate, then rise to 800 DEG C and high-temperature process 2h with 2 DEG C/min, is cooled to room
Temperature washes 12h, filtering, drying；
(5) in mass ratio it is that 1:5 is configured to mixed solution by obtained material after drying in step (4) and thiocarbamide, is transferred to anti-
Kettle is answered to carry out hydro-thermal reaction, temperature is 200 DEG C, and the time is that for 24 hours, filtering washes, is dry；
(6) obtained material is put into tube furnace after will be dry in step (5), in the protection that argon flow is 40cc/min
Under, 700 DEG C and high-temperature process 2h are risen to from room temperature with 5 DEG C/min of heating rate, is cooled to room temperature to get lithium ion battery
NiCo2S4/ graphene composite negative pole.
Embodiment 6
A kind of lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole, operating procedure are as follows:
(1) ion exchange resin is successively carried out to alkali process and acid processing, cleaning, drying；
(2) will it is dry in step (1) after gained ion exchange resin be added to 0.1mol/L nickel acetate tetrahydrate and
In the mixed solution of 0.2mol/L cobalt chloride hexahydrate, after stirring 12h, solution is removed, drying crushes；
(3) potassium hydroxide pore creating material is added in obtained material 1:2 in mass ratio after crushing in step (2), stirs evenly, and dries
It is dry；
(4) obtained material after drying in step (3) is put into tube furnace, in the protection that argon flow is 40cc/min
Under, 550 DEG C are risen to from room temperature with 5 DEG C/min of heating rate, then rise to 800 DEG C and high-temperature process 2h with 2 DEG C/min, is cooled to room
Temperature washes 12h, filtering, drying；
It (5) is in mass ratio that 1:4 is configured to mixed solution by obtained material after drying in step (4) and l-methionine,
It is transferred to reaction kettle and carries out hydro-thermal reaction, temperature is 200 DEG C, and the time is that for 24 hours, filtering washes, is dry；
(6) obtained material is put into tube furnace after will be dry in step (5), in the protection that argon flow is 40cc/min
Under, 700 DEG C and high-temperature process 2h are risen to from room temperature with 5 DEG C/min of heating rate, is cooled to room temperature to get lithium ion battery
NiCo2S4/ graphene composite negative pole.
Embodiment 7
A kind of lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole, operating procedure are as follows:
(1) ion exchange resin is successively carried out to alkali process and acid processing, cleaning, drying；
(2) will it is dry in step (1) after gained ion exchange resin be added to 0.1mol/L nickel acetate tetrahydrate and
In the mixed solution of 0.2mol/L cobalt chloride hexahydrate, after stirring 12h, solution is removed, drying crushes；
(3) potassium hydroxide pore creating material is added in obtained material 1:3 in mass ratio after crushing in step (2), stirs evenly, and dries
It is dry；
(4) obtained material after drying in step (3) is put into tube furnace, in the protection that argon flow is 40cc/min
Under, 550 DEG C are risen to from room temperature with 5 DEG C/min of heating rate, then rise to 850 DEG C and high-temperature process 2h with 2 DEG C/min, is cooled to room
Temperature washes 12h, filtering, drying；
(5) will in step (4) after drying obtained material with l-methionine to be in mass ratio that 1:4 is configured to mix molten
Liquid is transferred to reaction kettle and carries out hydro-thermal reaction, and temperature is 200 DEG C, and the time is that for 24 hours, filtering washes, is dry；
(6) obtained material is put into tube furnace after will be dry in step (5), in the protection that argon flow is 40cc/min
Under, 500 DEG C and high-temperature process 2h are risen to from room temperature with 5 DEG C/min of heating rate, is cooled to room temperature to get lithium ion battery
NiCo2S4/ graphene composite negative pole.
Embodiment 8
A kind of lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole, operating procedure are as follows:
(1) ion exchange resin is successively carried out to alkali process and acid processing, cleaning, drying；
(2) will it is dry in step (1) after gained ion exchange resin be added to 0.1mol/L nickel acetate tetrahydrate and
In the mixed solution of tetra- acetate hydrate cobalt of 0.2mol/L, after stirring 12h, solution is removed, drying crushes；
(3) potassium hydroxide pore creating material is added in obtained material 1:2 in mass ratio after crushing in step (2), stirs evenly, and dries
It is dry；
(4) obtained material after drying in step (3) is put into tube furnace, in the protection that argon flow is 40cc/min
Under, 550 DEG C are risen to from room temperature with 5 DEG C/min of heating rate, then rise to 850 DEG C and high-temperature process 2h with 2 DEG C/min, is cooled to room
Temperature washes 12h, filtering, drying；
(5) in mass ratio it is that 1:5 is configured to mixed solution by obtained material after drying in step (4) and cysteine, turns
Enter reaction kettle and carry out hydro-thermal reaction, temperature is 200 DEG C, and the time is that for 24 hours, filtering washes, is dry；
(6) obtained material is put into tube furnace after will be dry in step (5), in the protection that argon flow is 40cc/min
Under, 500 DEG C and high-temperature process 2h are risen to from room temperature with 5 DEG C/min of heating rate, is cooled to room temperature to get lithium ion battery
NiCo2S4/ graphene composite negative pole.
Embodiment 9
A kind of lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole, operating procedure are as follows:
(1) ion exchange resin is successively carried out to alkali process and acid processing, cleaning, drying；
(2) will it is dry in step (1) after gained ion exchange resin be added to 0.1mol/L nickel acetate tetrahydrate and
In the mixed solution of 0.2mol/L cobalt chloride hexahydrate, after stirring 12h, solution is removed, drying crushes；
(3) saleratus pore creating material is added in obtained material 1:3 in mass ratio after crushing in step (2), stirs evenly, and dries
It is dry；
(4) obtained material after drying in step (3) is put into tube furnace, in the protection that argon flow is 40cc/min
Under, 550 DEG C are risen to from room temperature with 5 DEG C/min of heating rate, then rise to 800 DEG C and high-temperature process 2h with 2 DEG C/min, is cooled to room
Temperature washes 12h, filtering, drying；
(5) in mass ratio it is that 1:5 is configured to mixed solution by obtained material after drying in step (4) and cysteine, turns
Enter reaction kettle and carry out hydro-thermal reaction, temperature is 200 DEG C, and the time is that for 24 hours, filtering washes, is dry；
(6) obtained material is put into tube furnace after will be dry in step (5), in the protection that argon flow is 40cc/min
Under, 700 DEG C and high-temperature process 2h are risen to from room temperature with 5 DEG C/min of heating rate, is cooled to room temperature to get lithium ion battery
NiCo2S4/ graphene composite negative pole.
Embodiment 10
A kind of lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole, operating procedure are as follows:
(1) ion exchange resin is successively carried out to alkali process and acid processing, cleaning, drying；
(2) will it is dry in step (1) after gained ion exchange resin be added to 0.1mol/L nickel acetate tetrahydrate and
In the mixed solution of tetra- acetate hydrate cobalt of 0.2mol/L, after stirring 12h, solution is removed, drying crushes；
(3) saleratus pore creating material is added in obtained material 1:1 in mass ratio after crushing in step (2), stirs evenly, and dries
It is dry；
(4) obtained material after drying in step (3) is put into tube furnace, in the protection that argon flow is 40cc/min
Under, 550 DEG C are risen to from room temperature with 5 DEG C/min of heating rate, then rise to 900 DEG C and high-temperature process 2h with 2 DEG C/min, is cooled to room
Temperature washes 12h, filtering, drying；
(5) in mass ratio it is that 1:5 is configured to mixed solution by obtained material after drying in step (4) and cysteine, turns
Enter reaction kettle and carry out hydro-thermal reaction, temperature is 180 DEG C, and the time is that for 24 hours, filtering washes, is dry；
(6) obtained material is put into tube furnace after will be dry in step (5), in the protection that argon flow is 40cc/min
Under, 500 DEG C and high-temperature process 2h are risen to from room temperature with 5 DEG C/min of heating rate, is cooled to room temperature to get lithium ion battery
NiCo2S4/ graphene composite negative pole.
The aforementioned description to specific exemplary embodiment of the invention is in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to the above instruction, can much be changed
And variation.The purpose of selecting and describing the exemplary embodiment is that explaining specific principle of the invention and its actually answering
With so that those skilled in the art can be realized and utilize a variety of different exemplary implementation schemes of the invention and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. a kind of lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole, which is characterized in that including following step
It is rapid:
(1) resin successively pre-processed, cleaned, dried；
(2) the gained resin of step (1) after dry is added in catalyst metal salt solution, which is that nickel salt is molten
The mixture of liquid and cobalt salt solution, stirring, drying crush；
(3) pore creating material is added in obtained material after crushing in step (2), stirs evenly, and dries；
(4) under the protection of inert atmosphere, 500-900 DEG C of high-temperature process 1-3h is cooled to obtained material after crushing step (3)
Room temperature, washing, filtering, drying；
(5) obtained material after drying in step (4) and sulfur-containing compound are configured to mixed solution, are transferred to reaction kettle and carry out hydro-thermal
Reaction, temperature are 160-200 DEG C, time 12-24h, filtering, washing, drying；
(6) for obtained material under the protection of inert atmosphere, 500-700 DEG C of high-temperature process 1-3h is cooling after will be dry in step (5)
To room temperature to get lithium ion battery NiCo2S4/ graphene composite negative pole.
2. lithium ion battery NiCo according to claim 12S4The preparation method of/graphene composite negative pole, feature
It is, resin described in step (1) is one of ion exchange resin, chelating resin, epoxy resin, phenolic resin or two
Kind or more mixture.
3. lithium ion battery NiCo according to claim 12S4The preparation method of/graphene composite negative pole, feature
It is, pretreatment described in step (1) is followed successively by alkali process and acid processing.
4. lithium ion battery NiCo according to claim 12S4The preparation method of/graphene composite negative pole, feature
It is, catalyst metals salinity is 0.05-0.2mol/L in step (2), and the catalyst metal salts are nickel salt, in cobalt salt
The molar ratio of two kinds of mixtures, nickel salt and cobalt salt mixing is 1:1-1:5；
Wherein, the nickel salt is nickel acetate tetrahydrate, Nickel dichloride hexahydrate, Nickelous nitrate hexahydrate or six hydration nickel sulfate；Institute
The cobalt salt stated is four acetate hydrate cobalts, cobalt chloride hexahydrate, cabaltous nitrate hexahydrate or Cobalt monosulfate heptahydrate.
5. lithium ion battery NiCo according to claim 12S4The preparation method of/graphene composite negative pole, feature
It is, the mass ratio of obtained material and pore creating material is 1:1-1:5 in step (3), and the pore creating material is potassium hydroxide, bicarbonate
The mixture of one or more of potassium, sodium hydroxide, sodium bicarbonate.
6. lithium ion battery NiCo according to claim 12S4The preparation method of/graphene composite negative pole, feature
It is, inert atmosphere described in step (4) is the mixture of one or more of argon gas, nitrogen, hydrogen or helium,
Inert atmosphere flow control is in 30~100cc/min.
7. lithium ion battery NiCo according to claim 12S4The preparation method of/graphene composite negative pole, feature
It is, high-temperature process described in step (4) is carried out in tube furnace or atmosphere Muffle furnace, the heating rate before high-temperature process
For 1-10 DEG C/min.
8. lithium ion battery NiCo according to claim 12S4The preparation method of/graphene composite negative pole, feature
It is, sulfur-containing compound described in step (5) is one or both of thiocarbamide, L-methionine, cysteine, cystine
Above mixture.
9. lithium ion battery NiCo according to claim 12S4The preparation method of/graphene composite negative pole, feature
It is, the mass ratio of obtained material and sulfur-containing compound is 1:1-1:5 after step (4) drying is added in step (5).
10. lithium ion battery NiCo according to claim 12S4The preparation method of/graphene composite negative pole, it is special
Sign is that inert atmosphere described in step (6) is the mixing of one or more of argon gas, nitrogen, hydrogen or helium
Object.
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