CN107611380A - A kind of preparation method of nickel oxide/stereochemical structure graphene composite material - Google Patents
A kind of preparation method of nickel oxide/stereochemical structure graphene composite material Download PDFInfo
- Publication number
- CN107611380A CN107611380A CN201710736645.5A CN201710736645A CN107611380A CN 107611380 A CN107611380 A CN 107611380A CN 201710736645 A CN201710736645 A CN 201710736645A CN 107611380 A CN107611380 A CN 107611380A
- Authority
- CN
- China
- Prior art keywords
- nickel
- graphene composite
- composite material
- stereochemical structure
- nickel oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to technical field of lithium ion, and in particular to a kind of nickel oxide/stereochemical structure graphene composite material is applied to the method for lithium ion battery negative material.The present invention is using polymer as carbon source, nickel salt is catalyst, by being calcined after being sufficiently mixed with pore creating material in tube furnace, after product is by washing the impurity such as the remaining pore creating material of removing, filter drying, nano nickel metallic particles/stereochemical structure graphene composite material is obtained, nickel oxide/stereochemical structure graphene composite material is prepared by hydro-thermal reaction and follow-up heat treatment in the material.Nickel oxide prepared by the present invention/stereochemical structure graphene composite material substantially increases the electric conductivity and structural stability of material；With good high rate performance and cyclical stability.Nickel oxide prepared by the present invention/stereochemical structure graphene composite material is bigger than surface, and yield is high, and technique is simple, it is easy to accomplish industrial mass production, is good lithium ion battery negative material.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of nickel oxide/stereochemical structure graphene composite wood
Method of the material applied to lithium ion battery negative material.
Background technology
With being continuously increased for Fossil fuel consumption, the problem of some are inevitable, such as environmental pollution, the energy are brought
Shortage, greenhouse effects etc..Therefore, develop new energy and effective energy storage device technology is extremely urgent.Lithium ion battery is considered as
One of most promising energy-storage system, because it has, transformation efficiency is high, and energy density is high, it is safe the advantages that and extensively should
For household electrical appliance and portable electric appts.At present, it is commercial mainly using graphite as lithium ion battery negative material, because
Have that cost is low for graphite, stable performance, the features such as coulombic efficiency is high.However, the theoretical capacity of graphite there was only 372mAh/g and
And high rate performance is poor.Therefore, in order to meet the needs of today's society continuous development, there is an urgent need to Development of Novel high-performance to bear for we
Pole material.Nickel oxide has higher theoretical capacity (718mAh/g) and volume energy density than graphite, but nickel oxide is conductive
Property is poor, and easily reunites in charge and discharge process, and volumetric expansion is serious.Therefore its as lithium ion battery negative material multiplying power with
Cyclical stability is poor, limits it and further applies.In order to solve these problems, we generally look for a kind of electric conductivity high, compare table
Carrier of the big material in face as nickel oxide.Graphene has high conductivity, high mechanical properties, high ratio as a kind of new material
The feature performance benefits such as surface, therefore be the ideal carrier of nickel oxide.But common two-dimensional graphene has easily reunion, preparation process
Complexity, the features such as low yield, limit performance and the practical application of some excellent properties.
In recent years, stereochemical structure graphene causes everybody attention, and it not only possesses the intrinsic excellent properties of graphene,
And its self supporting structure solves the problems, such as that two-dimensional graphene is easily reunited, the infiltration of electrolyte is more beneficial for, is lithium ion
Diffusion provides shorter path.Chemical vapour deposition technique (CVD) is the common method for preparing stereochemical structure graphene, but this method
Cost is high, low yield, it is difficult to commercial Application, and simple mixed oxidization nickel and stereochemical structure graphene, can not be fundamentally
Improve the performance of nickel oxide/stereochemical structure graphene composite material.Therefore, stereochemical structure graphene how is prepared on a large scale, it is excellent
Change the preparation method of nickel oxide/stereochemical structure graphene, be the problem of this area is in the urgent need to address.
In summary, this area still lacks one kind and can produced in enormous quantities, has high rate capability, long circulating stability
The method of nickel oxide/stereochemical structure graphene lithium ion battery negative material.
The information for being disclosed in the background section is merely intended to understanding of the increase to the general background of the present invention, without answering
It has been the prior art well known to persons skilled in the art when being considered as recognizing or implying the information structure in any form.
The content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art, there is provided one kind has height ratio capacity, high rate capability, and length is followed
The preparation method of the nickel oxide of ring stability/stereochemical structure graphene lithium ion battery negative material.
Technical scheme provided by the present invention is：
A kind of preparation method of lithium ion battery negative material nickel oxide/three-dimensional graphene composite material, including following step
Suddenly：
(1) first the polymer with ion-exchange capacity is pre-processed, washs, dries；
(2) pretreated polymer is added in 0.1-2.0mol/L nickel salt solution, after magnetic agitation 0.1-12h
Filter, remove filtrate；
(3) polymer in mass ratio 1 for having nickel ion will be exchanged in step (2):1-5 adds a certain amount of pore creating material, so
After add a certain amount of deionized water and pore creating material is dissolved just, be uniformly mixed, dry；
(4) by gained material in step (3) under protective atmosphere with 1-10 DEG C/min heating rate, be warming up to 400-
1000 DEG C, constant temperature 1-5h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary impurity；
Filter, drying, that is, obtain nano nickel metallic particles/three-dimensional graphene composite material；
(6) by the nano nickel metallic particles/three-dimensional graphene composite material being prepared in step (5) with it is certain density
It is transferred to after nickel salt and sulfate liquor are well mixed in reactor, heating response for a period of time, obtains sulfovinic acid nickel/three-dimensional
Graphene presoma；
(7) the sulfovinic acid nickel/three-dimensional grapheme presoma being prepared in step (6) is put into tube furnace, be passed through
Nitrogen gas, it is 200-1000 DEG C, constant temperature 1-10h to set heating-up temperature, and it is 1-10 DEG C/min to control heating rate, protective gas
Flow velocity is 0.1-1sccm/min, after natural cooling, obtains nickel oxide/three-dimensional graphene composite material.
Preferably, the pretreatment in the step (1) mixes for the one or more in heat treatment, acid treatment and alkali process
Close processing mode.
Preferably, polymer described in the step (1) is PKS polymer, 0017 strongly acidic styrene be sun from
Sub-exchange resin, D001 strong-acid cation-exchange resins, D403 chelating resins, D850 chelating resins, KP112 metallic nickels recovery tree
The mixture of fat and one or more of resins in KP752 metallic nickels recovery resin.
Preferably, the described nickel salt in the step (2) is in nickel chloride, nickel sulfate, nickel nitrate and nickel acetate
One or more of mixtures.
Preferably, the pore creating material described in step (3) includes ammonium hydrogen carbonate, sodium acid carbonate, potassium hydroxide, hydroxide
One or both of calcium, ammonium carbonate and sodium hydroxide thing mixed above.
Preferably, protective atmosphere described in step (4) be one kind in nitrogen, carbon dioxide, helium and argon gas or
Two or more mixtures.
Preferably, the sulfate described in step (6) is ferric sulfate, sodium sulphate, copper sulphate, potassium sulfate or zinc sulfate；
Described nickel salt is nickel chloride, nickel acetate or nickel nitrate；In mixed solution, sulfate liquor concentration is 0.01-1mol/L, nickel salt
Solution concentration is 0.01-0.5mol/L.
Preferably, the heating-up temperature described in step (6) is 100-200 DEG C, reaction time 2-48h.
Compared with prior art, the present invention has the advantages that：
(1) present invention promotes carbon source graphite, subtracted significantly at a lower temperature by the way that nickel ion is exchanged on polymer
Few energy consumption, nickel ion forms nano metal nickel particle by thermal reduction in addition, therefore nano metal nickel particle is utilized conjunction again
Into porous nickel oxide nanobelt.
(2) present invention is to promote to be embedded in the nano nickel metallic particles inside stereochemical structure graphene using in situ synthesis
Sulfovinic acid nickel nanobelt is grown under hydrothermal conditions, and further heat treatment forms porous nickel oxide nanobelt.The oxygen of preparation
Change nickel/stereochemical structure graphene composite material, porous nickel oxide nanobelt is built-in inside stereochemical structure graphene, therefore
The electric conductivity and structural stability of the material greatly improved.
(3) there are high mechanical properties and the stereochemical structure graphene of stereochemical structure frame structure, provided for nickel oxide slow
The place of punching, the nickel oxide volumetric expansion in charge and discharge process is avoided to cause active material to come off.
(4) nickel oxide/stereochemical structure graphene composite material prepared by the present invention, bigger than surface, yield is high, it is easy to accomplish
Industrial mass production.
(5) nickel oxide/stereochemical structure graphene composite material that the present invention is prepared by situ synthesis, gives full play to
The feature performance benefit of nickel oxide and stereochemical structure grapheme material, applied to negative electrode of lithium ion battery have good high rate performance and
Cyclical stability.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of nano nickel metallic particles/stereochemical structure grapheme material of preparation method of the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of sulfovinic acid nickel/stereochemical structure grapheme material of preparation method of the present invention；
Fig. 3 is the scanning electron microscope (SEM) photograph of nickel oxide/stereochemical structure grapheme material of preparation method of the present invention；
Fig. 4 is the projection electron microscope of nickel oxide/stereochemical structure grapheme material of preparation method of the present invention；
Fig. 5 is nickel oxide/stereochemical structure grapheme material of preparation method of the present invention as lithium ion battery negative material
High rate performance test curve；
Fig. 6 is nickel oxide/stereochemical structure grapheme material of preparation method of the present invention as lithium ion battery negative material
Cyclical stability test curve.
Embodiment
Presently preferred embodiments of the present invention is described in detail below in conjunction with the accompanying drawings, so that advantages and features of the invention energy
It is easier to be readily appreciated by one skilled in the art, apparent is clearly defined so as to be made to protection scope of the present invention.
Embodiment 1：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) PKS polymer is pre-processed first, washed, dried；
(2) pretreated PKS polymer is added in 2.0mol/L nickel chloride solution, taken out after mixing 12h
Filter, remove filtrate；
(3) the PKS polymer in mass ratio 1 for having nickel ion will be exchanged in step (2):1 adds a certain amount of potassium hydroxide,
Then adding a certain amount of deionized water makes potassium hydroxide dissolve just, is uniformly mixed, drying；
(4) gained material in step (3) is warming up to 850 DEG C, perseverance in a nitrogen atmosphere with 10 DEG C/min heating rate
Warm 2h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary hydroxide
The impurity such as potassium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) and material
Amount concentration be 0.05mol/L nickel nitrates and 0.03mol/L metabisulfite solutions it is well mixed after be transferred in reactor, heating response
For a period of time, sulfovinic acid nickel/stereochemical structure graphene presoma is obtained.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 600 DEG C, constant temperature 3h, it is 2 DEG C/min to control heating rate, and protective gas flow velocity is 0.5sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Embodiment 2：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) 0017 strongly acidic styrene type cation exchange resin is pre-processed first, washed, dried；
(2) pretreated 0017 strongly acidic styrene type cation exchange resin is added to 1.0mol/L nickel sulfate
In solution, filtered after mixing 10h, remove filtrate；
(3) exchange in step (2) there is into 0017 strongly acidic styrene type cation exchange resin of nickel ion in mass ratio
1:1 adds a certain amount of potassium hydroxide, and then adding a certain amount of deionized water makes potassium hydroxide dissolve just, is stirred
It is even, drying；
(4) gained material in step (3) under an argon atmosphere with 10 DEG C/min heating rate, is warming up to 1000 DEG C,
Constant temperature 4h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary hydroxide
The impurity such as potassium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) and material
Amount concentration be 0.1mol/L nickel acetates and 0.05mol/L copper-baths it is well mixed after be transferred in reactor, heating response
For a period of time, sulfovinic acid nickel/stereochemical structure graphene presoma is obtained.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 500 DEG C, constant temperature 5h, it is 3 DEG C/min to control heating rate, and protective gas flow velocity is 0.5sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Embodiment 3：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) D001 strong-acid cation-exchange resins are pre-processed first, washed, dried；
(2) pretreated D001 strong-acid cation-exchange resins are added in 1mol/L nickel acetate solution, mixed
Filtered after stirring 10h, remove filtrate；
(3) the D001 strong-acid cation-exchange resins in mass ratio 1 for having nickel ion will be exchanged in step (2):1 adds necessarily
The calcium hydroxide of amount, then adding a certain amount of deionized water makes calcium hydroxide dissolve just, is uniformly mixed, drying；
(4) by gained material in step (3) under helium atmosphere with 5 DEG C/min heating rate, be warming up to 900 DEG C, it is permanent
Warm 3h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary hydroxide
The impurity such as calcium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) and material
Amount concentration be 0.1mol/L nickel acetates and 0.05mol/L ferrum sulfuricum oxydatum solutums it is well mixed after be transferred in reactor, heating response
For a period of time, sulfovinic acid nickel/stereochemical structure graphene presoma is obtained.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 600 DEG C, constant temperature 3h, it is 2 DEG C/min to control heating rate, and protective gas flow velocity is 0.5sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Embodiment 4：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) D403 chelating resins are pre-processed first, washed, dried；
(2) pretreated D403 chelating resins are added in 0.9mol/L nickel nitrate solution, after mixing 12h
Filter, remove filtrate；
(3) the D403 chelating resins in mass ratio 1 for having nickel ion will be exchanged in step (2):2 add a certain amount of carbonic acid
Ammonium, then adding a certain amount of deionized water makes ammonium carbonate dissolve just, is uniformly mixed, drying；
(4) gained material in step (3) is warming up to 800 DEG C, perseverance in a nitrogen atmosphere with 5 DEG C/min heating rate
Warm 2h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary ammonium carbonate
Deng impurity.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) and material
Amount concentration be 0.1mol/L nickel chlorides and 0.1mol/L ferrum sulfuricum oxydatum solutums it is well mixed after be transferred in reactor, heating response one
The section time, obtain sulfovinic acid nickel/stereochemical structure graphene presoma.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 600 DEG C, constant temperature 4h, it is 5 DEG C/min to control heating rate, and protective gas flow velocity is 0.5sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Embodiment 5：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) D850 chelating resins are pre-processed first, washed, dried；
(2) pretreated D850 chelating resins are added in 0.5mol/L nickel chloride solution, after mixing 12h
Filter, remove filtrate；
(3) the D850 chelating resins in mass ratio 1 for having nickel ion will be exchanged in step (2):2 add a certain amount of hydroxide
Sodium, then adding a certain amount of deionized water makes sodium hydroxide dissolve just, is uniformly mixed, drying；
(4) gained material in step (3) is warming up to 850 DEG C, perseverance under an argon atmosphere with 10 DEG C/min heating rate
Warm 3h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary hydroxide
The impurity such as sodium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the amount of the nano nickel metallic particles being prepared in step (5)/stereochemical structure graphene composite material material
Concentration be 0.05mol/L nickel nitrates and 0.05mol/L ferrum sulfuricum oxydatum solutums it is well mixed after be transferred in reactor, heating response one
The section time, obtain sulfovinic acid nickel/stereochemical structure graphene presoma.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 700 DEG C, constant temperature 2h, it is 5 DEG C/min to control heating rate, and protective gas flow velocity is 0.5sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Embodiment 6：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) KP112 metallic nickels recovery resin is pre-processed first, washs, dry；
(2) pretreated KP112 metallic nickels recovery resin is added in 2.0mol/L nickel nitrate solution, mixing is stirred
Filtered after mixing 12h, remove filtrate；
(3) the KP112 metallic nickels recovery resin in mass ratio 1 for having nickel ion will be exchanged in step (2):3 additions are a certain amount of
Potassium hydroxide, then adding a certain amount of deionized water makes potassium hydroxide dissolve just, is uniformly mixed, drying；
(4) gained material in step (3) is warming up to 900 DEG C, perseverance in a nitrogen atmosphere with 5 DEG C/min heating rate
Warm 2h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary hydroxide
The impurity such as potassium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) and material
Amount concentration be 0.0 5mol/L nickel acetates and 0.025mol/L potassium sulfate solutions it is well mixed after be transferred in reactor, heating is anti-
Sulfovinic acid nickel/stereochemical structure graphene presoma should be obtained for a period of time.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 900 DEG C, constant temperature 2h, it is 5 DEG C/min to control heating rate, and protective gas flow velocity is 0.5sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Embodiment 7：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) KP752 metallic nickels recovery resin is pre-processed first, washs, dry；
(2) pretreated KP752 metallic nickels recovery resin is added in 1mol/L nickel nitrate solution, mixed
Filtered after 12h, remove filtrate；
(3) the KP752 metallic nickels recovery resin in mass ratio 1 for having nickel ion will be exchanged in step (2):3 additions are a certain amount of
Potassium hydroxide, then adding a certain amount of deionized water makes potassium hydroxide dissolve just, is uniformly mixed, drying；
(4) gained material in step (3) is warming up to 1000 DEG C, perseverance under an argon atmosphere with 3 DEG C/min heating rate
Warm 2h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary hydroxide
The impurity such as potassium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) and material
Amount concentration be 0.05mol/L nickel chlorides and 0.05mol/L solution of zinc sulfate it is well mixed after be transferred in reactor, heating response
For a period of time, sulfovinic acid nickel/stereochemical structure graphene presoma is obtained.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 600 DEG C, constant temperature 2h, it is 3 DEG C/min to control heating rate, and protective gas flow velocity is 1sccm/min.Oxygen is obtained after natural cooling
Change nickel/stereochemical structure graphene composite material.
Embodiment 8：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) PKS polymer is pre-processed first, washed, dried；
(2) pretreated PKS polymer is added in 1.0mol/L nickel chloride solution, taken out after mixing 10h
Filter, remove filtrate；
(3) the PKS polymer in mass ratio 1 for having nickel ion will be exchanged in step (2):3 add a certain amount of potassium hydroxide,
Then adding a certain amount of deionized water makes potassium hydroxide dissolve just, is uniformly mixed, drying；
(4) gained material in step (3) is warming up to 900 DEG C, perseverance in a nitrogen atmosphere with 5 DEG C/min heating rate
Warm 3h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary hydroxide
The impurity such as potassium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) and material
Amount concentration be 0.05mol/L nickel acetates and 0.03mol/L solution of zinc sulfate it is well mixed after be transferred in reactor, heating response
For a period of time, sulfovinic acid nickel/stereochemical structure graphene presoma is obtained.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 700 DEG C, constant temperature 4h, it is 3 DEG C/min to control heating rate, and protective gas flow velocity is 0.5sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Embodiment 9：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) 0017 strongly acidic styrene type cation exchange resin is pre-processed first, washed, dried；
(2) pretreated 0017 strongly acidic styrene type cation exchange resin is added to 0.5mol/L nickel sulfate
In solution, filtered after mixing 8h, remove filtrate；
(3) exchange in step (2) there is into 0017 strongly acidic styrene type cation exchange resin of nickel ion in mass ratio
1:4 add a certain amount of potassium hydroxide, and then adding a certain amount of deionized water makes potassium hydroxide dissolve just, are stirred
It is even, drying；
(4) gained material in step (3) is warming up to 900 DEG C, perseverance in a nitrogen atmosphere with 10 DEG C/min heating rate
Warm 3h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary hydroxide
The impurity such as potassium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) and material
Amount concentration be 0.04mol/L nickel nitrates and 0.02mol/L metabisulfite solutions it is well mixed after be transferred in reactor, heating response
For a period of time, sulfovinic acid nickel/stereochemical structure graphene presoma is obtained.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 700 DEG C, constant temperature 3h, it is 5 DEG C/min to control heating rate, and protective gas flow velocity is 0.3sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Embodiment 10：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) KP752 metallic nickels recovery resin is pre-processed first, washs, dry；
(2) pretreated KP752 metallic nickels recovery resin is added in 0.5mol/L nickel nitrate solution, mixing is stirred
Filtered after mixing 12h, remove filtrate；
(3) the KP752 metallic nickels recovery resin in mass ratio 1 for having nickel ion will be exchanged in step (2):4 additions are a certain amount of
Potassium hydroxide, then adding a certain amount of deionized water makes potassium hydroxide dissolve just, is uniformly mixed, drying；
(4) gained material in step (3) is warming up to 900 DEG C, perseverance in a nitrogen atmosphere with 5 DEG C/min heating rate
Warm 2h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary hydroxide
The impurity such as potassium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) and material
Amount concentration be 0.05mol/L nickel chlorides and 0.025mol/L metabisulfite solutions it is well mixed after be transferred in reactor, heating is anti-
Sulfovinic acid nickel/stereochemical structure graphene presoma should be obtained for a period of time.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 600 DEG C, constant temperature 4h, it is 5 DEG C/min to control heating rate, and protective gas flow velocity is 0.5sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Embodiment 11：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) PKS polymer is pre-processed first, washed, dried；
(2) pretreated PKS polymer is added in 2.0mol/L nickel sulfate solution, taken out after mixing 12h
Filter, remove filtrate；
(3) the PKS polymer in mass ratio 1 for having nickel ion will be exchanged in step (2):5 add a certain amount of ammonium hydrogen carbonate,
Then adding a certain amount of deionized water makes ammonium hydrogen carbonate dissolve just, is uniformly mixed, drying；
(4) gained material in step (3) is warming up to 900 DEG C, perseverance under an argon atmosphere with 5 DEG C/min heating rate
Warm 2h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary bicarbonate
The impurity such as ammonium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) and material
Amount concentration be 0.1mol/L nickel chlorides and 0.05mol/L ferrum sulfuricum oxydatum solutums it is well mixed after be transferred in reactor, heating response
For a period of time, sulfovinic acid nickel/stereochemical structure graphene presoma is obtained.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 800 DEG C, constant temperature 3h, it is 10 DEG C/min to control heating rate, and protective gas flow velocity is 1sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Embodiment 12：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) D850 chelating resins are pre-processed first, washed, dried；
(2) pretreated D850 chelating resins are added in 2.0mol/L nickel acetate solution, after mixing 12h
Filter, remove filtrate；
(3) the D850 chelating resins in mass ratio 1 for having nickel ion will be exchanged in step (2):4 add a certain amount of bicarbonate
Sodium, then adding a certain amount of deionized water makes sodium acid carbonate dissolve just, is uniformly mixed, drying；
(4) gained material in step (3) is warming up to 850 DEG C, perseverance under an argon atmosphere with 10 DEG C/min heating rate
Warm 2h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary bicarbonate
The impurity such as sodium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) and material
Amount concentration be 0.2mol/L nickel acetates and 0.1mol/L ferrum sulfuricum oxydatum solutums it is well mixed after be transferred in reactor, heating response one
The section time, obtain sulfovinic acid nickel/stereochemical structure graphene presoma.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 700 DEG C, constant temperature 3h, it is 2 DEG C/min to control heating rate, and protective gas flow velocity is 0.5sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Embodiment 13：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) D001 strong-acid cation-exchange resins are pre-processed first, washed, dried；
(2) pretreated D001 strong-acid cation-exchange resins are added in 1.0mol/L nickel nitrate solution, mixed
Filtered after closing stirring 10h, remove filtrate；
(3) the D001 strong-acid cation-exchange resins in mass ratio 1 for having nickel ion will be exchanged in step (2):5 add necessarily
The potassium hydroxide of amount, then adding a certain amount of deionized water makes potassium hydroxide dissolve just, is uniformly mixed, drying；
(4) gained material in step (3) is warming up to 900 DEG C, perseverance under an argon atmosphere with 10 DEG C/min heating rate
Warm 2h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary hydroxide
The impurity such as potassium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) and material
Amount concentration be 0.05mol/L nickel acetates and 0.05mol/L copper-baths it is well mixed after be transferred in reactor, heating response
For a period of time, sulfovinic acid nickel/stereochemical structure graphene presoma is obtained.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 700 DEG C, constant temperature 5h, it is 5 DEG C/min to control heating rate, and protective gas flow velocity is 0.5sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Embodiment 14：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) D403 chelating resins are pre-processed first, washed, dried；
(2) pretreated D403 chelating resins are added in 1.0mol/L nickel acetate solution, after mixing 12h
Filter, remove filtrate；
(3) the D403 chelating resins in mass ratio 1 for having nickel ion will be exchanged in step (2):3 add a certain amount of hydroxide
Potassium, then adding a certain amount of deionized water makes potassium hydroxide dissolve just, is uniformly mixed, drying；
(4) gained material in step (3) is warming up to 900 DEG C, perseverance in a nitrogen atmosphere with 1 DEG C/min heating rate
Warm 3h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary hydroxide
The impurity such as potassium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) and material
Amount concentration be 0.05mol/L nickel nitrates and 0.03mol/L solution of zinc sulfate it is well mixed after be transferred in reactor, heating response
For a period of time, sulfovinic acid nickel/stereochemical structure graphene presoma is obtained.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 700 DEG C, constant temperature 1h, it is 3 DEG C/min to control heating rate, and protective gas flow velocity is 0.2sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Embodiment 15：
A kind of preparation method of lithium ion battery nickel oxide/stereochemical structure graphene negative material, comprises the following steps：
(1) KP112 metallic nickels recovery resin is pre-processed first, washs, dry；
(2) pretreated KP112 metallic nickels recovery resin is added in 0.5mol/L nickel acetate solution, mixing is stirred
Filtered after mixing 8h, remove filtrate；
(3) the KP112 metallic nickels recovery resin in mass ratio 1 for having nickel ion will be exchanged in step (2):2 additions are a certain amount of
Sodium hydroxide, then adding a certain amount of deionized water makes sodium hydroxide dissolve just, is uniformly mixed, drying；
(4) by gained material in step (3) under carbon dioxide atmosphere with 5 DEG C/min heating rate, be warming up to 800
DEG C, constant temperature 3h；
(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary hydroxide
The impurity such as sodium.Filter, drying, that is, obtain nano nickel metallic particles/stereochemical structure graphene composite material.
(6) by the nano nickel metallic particles/stereochemical structure graphene composite material being prepared in step (5) with it is certain dense
It is transferred to after the nickel nitrate and ferrum sulfuricum oxydatum solutum of degree are well mixed in reactor, heating response for a period of time, obtains sulfovinic acid
Nickel/stereochemical structure graphene presoma.
(7) presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen gas, heating-up temperature is set
For 700 DEG C, constant temperature 2h, it is 3 DEG C/min to control heating rate, and protective gas flow velocity is 0.5sccm/min.Obtained after natural cooling
Nickel oxide/stereochemical structure graphene composite material.
Respectively the yield to nickel oxide/stereochemical structure graphene composite material for being prepared in embodiment 1-15, compare table
Area, tap density are tested, and the results are shown in Table 1.
The physical parameter for nickel oxide/stereochemical structure graphene composite material that the preparation method of the present invention of table 1 obtains
| Processing | Yield (%) | Specific surface area (m2g-1) | Tap density (mg cm-3) |
| Embodiment 1 | 23.5 | 648 | 135.2 |
| Embodiment 2 | 21.3 | 703 | 126.1 |
| Embodiment 3 | 22.1 | 689 | 131.4 |
| Embodiment 4 | 18.2 | 854 | 110.5 |
| Embodiment 5 | 17.9 | 861 | 108.2 |
| Embodiment 6 | 15.1 | 920 | 95.3 |
| Embodiment 7 | 14.9 | 931 | 92.5 |
| Embodiment 8 | 15.3 | 915 | 96.1 |
| Embodiment 9 | 12.1 | 1121 | 85.1 |
| Embodiment 10 | 11.8 | 1210 | 82.3 |
| Embodiment 11 | 9.5 | 1380 | 74.6 |
| Embodiment 12 | 12.5 | 1161 | 85.3 |
| Embodiment 13 | 10.0 | 1375 | 75.1 |
| Embodiment 14 | 15.1 | 970 | 94.7 |
| Embodiment 15 | 18.3 | 862 | 109.3 |
As shown in Table 1, nickel oxide/stereochemical structure graphene composite material that the present invention obtains, by changing preparation technology,
Obtained nickel oxide/stereochemical structure graphene composite material yield, specific surface area, tap density are all different.With pore-creating
The increase of agent, the sample yield being prepared is lower, and specific surface area is bigger, and tap density is smaller.
As shown in figure 1, nano nickel metallic particles/three-dimensional grapheme material that in preparation method of the present invention prepared by step (5)
Scanning electron microscope (SEM) photograph, it can clearly be seen that stereochemical structure graphene coated metal nickel particle, illustrate the metallic nickel as nickel source
Grain is covered by inside graphene.
As shown in Fig. 2 sulfovinic acid nickel/stereochemical structure graphene scanning electricity prepared by preparation method step (6) of the present invention
Mirror figure, sulfovinic acid nickel nanobelt and stereochemical structure graphene are closely combined together, and this is advantageous to the structure for improving material
Stability.
As shown in Figure 3-4, the scanning electricity of nickel oxide/stereochemical structure graphene prepared by preparation method step (7) of the present invention
Mirror figure and projection electron microscope, it can be seen that nickel oxide nano band is porous, and stereochemical structure graphene links together, this
With the scanning electron microscope (SEM) photograph consistent appearance shown in Fig. 2.
As seen in figs. 5-6, nickel oxide/stereochemical structure graphene that prepared by preparation method step (7) of the present invention as lithium from
The high rate performance and stable circulation linearity curve of sub- cell negative electrode material test, illustrate nickel oxide/stereochemical structure graphene composite wood
Material has high rate capability and long circulating stability as lithium ion battery negative material.
The description of the foregoing specific illustrative embodiment to the present invention is to illustrate and the purpose of illustration.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, can be much changed
And change.The purpose of selecting and describing the exemplary embodiment is that explain that the certain principles of the present invention and its reality should
With so that those skilled in the art can realize and utilize the present invention a variety of exemplaries and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (8)
- A kind of 1. preparation method of lithium ion battery negative material nickel oxide/three-dimensional graphene composite material, it is characterised in that bag Include following steps：(1) first the polymer with ion-exchange capacity is pre-processed, washs, dries；(2) pretreated polymer is added in 0.1-2.0mol/L nickel salt solution, taken out after magnetic agitation 0.1-12h Filter, remove filtrate；(3) polymer in mass ratio 1 for having nickel ion will be exchanged in step (2):1-5 adds a certain amount of pore creating material, Ran Houjia Entering a certain amount of deionized water makes pore creating material dissolve just, is uniformly mixed, drying；(4) by gained material in step (3) under protective atmosphere with 1-10 DEG C/min heating rate, be warming up to 400-1000 DEG C, constant temperature 1-5h；(5) gained material spends ionized water cleaning several times after heating in step (4), removes unnecessary impurity；Filter, Drying, that is, obtain nano nickel metallic particles/three-dimensional graphene composite material；(6) by the nano nickel metallic particles/three-dimensional graphene composite material being prepared in step (5) and certain density nickel salt It is transferred to after being well mixed with sulfate liquor in reactor, heating response for a period of time, obtains sulfovinic acid nickel/three-dimensional graphite Alkene presoma；(7) the sulfovinic acid nickel/three-dimensional grapheme presoma being prepared in step (6) is put into tube furnace, is passed through nitrogen Gas, it is 200-1000 DEG C, constant temperature 1-10h to set heating-up temperature, and it is 1-10 DEG C/min to control heating rate, protective gas flow velocity For 0.1-1sccm/min, after natural cooling, nickel oxide/three-dimensional graphene composite material is obtained.
- 2. the preparation side of lithium ion battery negative material nickel oxide/three-dimensional graphene composite material according to claim 1 Method, it is characterised in that the pretreatment in the step (1) is one or more of mixing in heat treatment, acid treatment and alkali process Processing mode.
- 3. the preparation side of lithium ion battery negative material nickel oxide/three-dimensional graphene composite material according to claim 1 Method, it is characterised in that the polymer described in the step (1) is PKS polymer, 0017 strongly acidic styrene's cation is handed over Change resin, D001 strong-acid cation-exchange resins, D403 chelating resins, D850 chelating resins, KP112 metallic nickels recovery resin and The mixture of one or more of resins in KP752 metallic nickels recovery resin.
- 4. the preparation side of lithium ion battery negative material nickel oxide/three-dimensional graphene composite material according to claim 1 Method, it is characterised in that the described nickel salt in the step (2) is one kind in nickel chloride, nickel sulfate, nickel nitrate and nickel acetate Or several mixture.
- 5. the preparation side of lithium ion battery negative material nickel oxide/three-dimensional graphene composite material according to claim 1 Method, it is characterised in that the pore creating material described in step (3) includes ammonium hydrogen carbonate, sodium acid carbonate, potassium hydroxide, calcium hydroxide, carbon One or both of sour ammonium and sodium hydroxide thing mixed above.
- 6. the preparation side of lithium ion battery negative material nickel oxide/three-dimensional graphene composite material according to claim 1 Method, it is characterised in that the protective atmosphere described in step (4) is one or both of nitrogen, carbon dioxide, helium and argon gas Mixture above.
- 7. the preparation side of lithium ion battery negative material nickel oxide/three-dimensional graphene composite material according to claim 1 Method, it is characterised in that the sulfate described in step (6) is ferric sulfate, sodium sulphate, copper sulphate, potassium sulfate or zinc sulfate；It is described Nickel salt be nickel chloride, nickel acetate or nickel nitrate；In mixed solution, sulfate liquor concentration is 0.01-1mol/L, nickel salt solution Concentration is 0.01-0.5mol/L.
- 8. the preparation side of lithium ion battery negative material nickel oxide/three-dimensional graphene composite material according to claim 1 Method, it is characterised in that the heating-up temperature described in step (6) is 100-200 DEG C, reaction time 2-48h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710736645.5A CN107611380B (en) | 2017-08-24 | 2017-08-24 | Preparation method of nickel oxide/graphene composite material with three-dimensional structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710736645.5A CN107611380B (en) | 2017-08-24 | 2017-08-24 | Preparation method of nickel oxide/graphene composite material with three-dimensional structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107611380A true CN107611380A (en) | 2018-01-19 |
| CN107611380B CN107611380B (en) | 2020-06-26 |
Family
ID=61065640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710736645.5A Active CN107611380B (en) | 2017-08-24 | 2017-08-24 | Preparation method of nickel oxide/graphene composite material with three-dimensional structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107611380B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108423665A (en) * | 2018-05-02 | 2018-08-21 | 广西大学 | A kind of D structure graphene powder material and optimization production method |
| CN109768233A (en) * | 2018-12-12 | 2019-05-17 | 广西大学 | Lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole |
| CN110788344A (en) * | 2019-09-27 | 2020-02-14 | 天津大学 | Preparation method for loading metal nanoparticles with different contents on surface of graphene |
| CN111924897A (en) * | 2020-08-07 | 2020-11-13 | 厦门厦钨新能源材料股份有限公司 | Lithium ion battery material precursor and preparation method thereof |
| CN113756090A (en) * | 2021-09-10 | 2021-12-07 | 山西新华防化装备研究院有限公司 | Preparation method and application of electromagnetic shielding function layer material |
| CN113752640A (en) * | 2021-09-10 | 2021-12-07 | 山西新华防化装备研究院有限公司 | Lightweight electromagnetic shielding tarpaulin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090305135A1 (en) * | 2008-06-04 | 2009-12-10 | Jinjun Shi | Conductive nanocomposite-based electrodes for lithium batteries |
| US20160043384A1 (en) * | 2014-08-07 | 2016-02-11 | Aruna Zhamu | Graphene foam-protected anode active materials for lithium batteries |
| CN106829914A (en) * | 2017-01-22 | 2017-06-13 | 广西大学 | A kind of three-dimensional porous carbon negative pole material of lithium ion battery |
-
2017
- 2017-08-24 CN CN201710736645.5A patent/CN107611380B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090305135A1 (en) * | 2008-06-04 | 2009-12-10 | Jinjun Shi | Conductive nanocomposite-based electrodes for lithium batteries |
| US20160043384A1 (en) * | 2014-08-07 | 2016-02-11 | Aruna Zhamu | Graphene foam-protected anode active materials for lithium batteries |
| CN106829914A (en) * | 2017-01-22 | 2017-06-13 | 广西大学 | A kind of three-dimensional porous carbon negative pole material of lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 王星辉: "锂离子电池金属氧化物阳极的纳米结构设计与制备", 《中国博士学位论文全文数据库工程科技Ⅱ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108423665A (en) * | 2018-05-02 | 2018-08-21 | 广西大学 | A kind of D structure graphene powder material and optimization production method |
| CN109768233A (en) * | 2018-12-12 | 2019-05-17 | 广西大学 | Lithium ion battery NiCo2S4The preparation method of/graphene composite negative pole |
| CN109768233B (en) * | 2018-12-12 | 2021-03-26 | 广西大学 | NiCo of lithium ion battery2S4Preparation method of/graphene composite negative electrode material |
| CN110788344A (en) * | 2019-09-27 | 2020-02-14 | 天津大学 | Preparation method for loading metal nanoparticles with different contents on surface of graphene |
| CN111924897A (en) * | 2020-08-07 | 2020-11-13 | 厦门厦钨新能源材料股份有限公司 | Lithium ion battery material precursor and preparation method thereof |
| CN113756090A (en) * | 2021-09-10 | 2021-12-07 | 山西新华防化装备研究院有限公司 | Preparation method and application of electromagnetic shielding function layer material |
| CN113752640A (en) * | 2021-09-10 | 2021-12-07 | 山西新华防化装备研究院有限公司 | Lightweight electromagnetic shielding tarpaulin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107611380B (en) | 2020-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107611380A (en) | A kind of preparation method of nickel oxide/stereochemical structure graphene composite material | |
| CN106410152B (en) | A kind of one-dimensional antimony trisulfide-carbon composite, preparation method and application | |
| CN106829914A (en) | A kind of three-dimensional porous carbon negative pole material of lithium ion battery | |
| CN103318978B (en) | Preparation method of mesoporous nickel cobaltate fiber and application thereof | |
| CN104971760B (en) | The preparation method of sulfur-bearing, nitrogen and transition metal macropore carbon oxygen reduction catalyst | |
| CN109148903A (en) | The preparation method of the spherical carbon-based nickel cobalt bimetallic oxide composite material of 3D sea urchin | |
| CN107226475A (en) | A kind of kalium ion battery positive electrode and preparation method thereof and kalium ion battery | |
| CN107959006A (en) | A kind of lignin-base hard carbon/carbon nano tube compound material and preparation method thereof and the application in lithium ion battery negative material | |
| CN110474057A (en) | A kind of preparation method and application of the oxygen reduction electro-catalyst based on lignocellulose-like biomass carbon | |
| CN107082453B (en) | The preparation of hydrated iron barium oxide as water system Magnesium ion battery negative electrode material and application method | |
| CN105047435A (en) | Manganese-metal-organic-framework electrode material, and preparation method and application thereof | |
| CN107140608B (en) | A kind of method of the ultra-dispersed antimony selenide nano wire of ultrasonic wave auxiliary water hot preparation sodium-ion battery cathode | |
| CN107369821A (en) | A kind of ultrafast method for preparing ferroso-ferric oxide/graphene lithium ion battery composite negative pole material | |
| CN106345501A (en) | Method for preparing iron phosphide based on magnetic ionic liquid modified carbon nanotube composite, and products and application thereof | |
| CN105140494A (en) | Biomimetic synthesis method of Fe3O4/Fe/C nano composite battery electrode material | |
| CN104129778A (en) | Preparation method of functionalized graphene used for positive electrode material of lithium ion battery | |
| CN110624540A (en) | Novel ruthenium-based self-supporting electro-catalytic material, preparation method thereof and application thereof in electro-catalytic nitrogen reduction for producing ammonia | |
| CN109665525A (en) | A kind of preparation method of " dumbbell shape " iron nitrogen codope porous carbon | |
| CN110492076B (en) | Preparation method of two-dimensional porous hexagonal metal oxide nanosheet composite material and application of composite material in potassium ion battery | |
| CN108598448A (en) | A kind of three-dimensional structure carbon coating cobalt acid manganese nano-material and preparation method and application | |
| CN107785589A (en) | A kind of preparation method of iron cobalt compound@bacteria cellulose lithium air battery positive electrode materials | |
| CN103066249B (en) | Cobalt-based complex oxide/graphene composite material as well as preparation method and application thereof | |
| CN109046394B (en) | Hollow tubular CoSe2Nano material and preparation method and application thereof | |
| CN106981650A (en) | A kind of preparation method of nanoscale bismuth with elementary | |
| CN110350187A (en) | A kind of stratiform ternary sodium-ion battery method for preparing anode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |