CN104701035A - Preparation method of metal oxide/graphene or multi-metal oxide/graphene composite electrode material - Google Patents
Preparation method of metal oxide/graphene or multi-metal oxide/graphene composite electrode material Download PDFInfo
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- CN104701035A CN104701035A CN201510124764.6A CN201510124764A CN104701035A CN 104701035 A CN104701035 A CN 104701035A CN 201510124764 A CN201510124764 A CN 201510124764A CN 104701035 A CN104701035 A CN 104701035A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
Abstract
The invention discloses a preparation method of a composite electric material containing nonmetallic oxides, metal oxides and/or multi-metal oxides and graphene. The method comprises preparing graphene oxide suspension, taking nonmetallic hydrates, metal hydrates and/or multi-metal hydrates as the precursor, uniformly mixing the suspension and the precursor and moving the mixture into a hydrothermal reactor, maintaining a certain temperature for hours to subject graphene oxide to reduction reaction and the metal hydrates or multi-metal hydrates to oxidation reaction, and meanwhile, dehydrating the reactants to obtain a metal oxide/graphene or multi-metal oxide/graphene composite electrode material. The preparation method is simple and rapid in process and can obtain the metal oxide/graphene or multi-metal oxide/graphene composite electrode material simply through one hydrothermal reaction; the preparation process is pollution-free and low in energy consumption; the obtained composite material is high in conductivity and capacity, excellent in charge-discharge circulating performance and applicable to mass industrial production.
Description
Technical field
The invention belongs to Material Field, be specifically related to the preparation method of a kind of metal oxide/Graphene or poly-metal deoxide/graphene combination electrode material.
Background technology
Metal oxide often possesses special physicochemical properties, cheap, environmental friendliness, potential window are wider, ratio capacitance advantages of higher, be widely used in the fields such as secondary cell, ultracapacitor, catalysis, in addition, they have also showed potential using value in fields such as sensing, magnetics and microwave absorptions.In recent years, the electrode material developing a kind of cheapness becomes the emphasis of research.The preparation method current as electrode material mainly contains: high temperature solid-state method, sol-gal process, coprecipitation.These method techniques are more complicated, cost is higher, as L.Guohua discloses with LiCO
3and MnO
2for raw material Hybrid Heating 48h, when temperature is 800 DEG C, chemical property is best; Sol-gal process presoma is long for drying time, and needs more than high-temperature calcination 10h; Prepare the method for respective substance, and calcining generally needs high temperature 750 DEG C ~ 900 DEG C.
In addition, also there are main three large problems in the electrode material that prior art prepares: one is that capacity is lower, still can not practical requirement, and its discharge capacity is main relevant with its specific area; In addition it is also closely related with factors such as the carrying capacity of metal oxide in the crystal formation of material, microscopic appearance, pore-size distribution, electrode; Two is that metal oxide usual own electronic conductance is lower, is difficult to adapt to high current charge-discharge; Three is that its cyclical stability is poor, has much room for improvement, the invertibity that cyclical stability and surface oxidation reduction react this also indirectly cause its material property poor.
For above defect, be necessary to develop a kind of Large ratio surface, high conductivity, the preparation method of the new electrode materials of high power capacity, to meet the needs of actual production.
Summary of the invention
The present invention prepares lithium ion battery and capacitor electrode material with the compound of metal hydrate and many metal hydrates and graphene oxide, and the method preparation technology is simple, reactant low price, is applicable to large-scale industrial production; Production process is pollution-free, power consumption is few, the Graphene of the composite material obtained and current bibliographical information simply mix or oxide particle is coated on pattern and has a great difference, in addition, the graphene oxide of pre-compound and hydrate thereof be carry out in pretreated pure substance thus product not only purity is high, and epigranular, specific area is large, good conductivity, capacity is high, and good cycle.
Method provided by the invention comprises:
By the suspension-turbid liquid of metal hydrate and/or many metal hydrates or solution and graphene oxide solution according to volume ratio 1-5:0.05-1, or after the suspension-turbid liquid of the hydrate of nonmetal oxide or solution mixes according to the volume ratio of 1-5:0.05 ~ 1 with graphene oxide solution respectively, hydro-thermal reaction a few hours at 100-300 DEG C, obtain containing nonmetal oxide, containing metal oxide and/or poly-metal deoxide, with graphene combination electrode material.
In hydrothermal reaction process, graphene oxide generation reduction reaction, metal hydrate or many metal hydrates generation oxidation reaction, the dehydration of simultaneous reactions thing generates product.
Preferably, described method also comprises: after the product separation liquid phase of hydro-thermal reaction, and solid phase, in 100 ~ 800 DEG C of activation a few hours (0.5-20h), obtains containing metal oxide or poly-metal deoxide/graphene combination electrode material.By this step process, the electrode material that performance improves further can be obtained.Such material not only as the positive and negative electrode material of Non-aqueous lithium battery, can also be used as the electrode material of aqueous solution ultracapacitor respectively.
Preferably, described metal hydrate is compd A Om (OH) n (H with following general formula
2o) q, described metal element A is chromium, cobalt, nickel, molybdenum, manganese, copper, tin, titanium, cadmium or vanadium, is 0 when in formula, n with q is different, such as FeO (OH), Fe (OH)
3(H
2o)
0.25etc. serial ferrous metal hydrate, the series such as CoO (OH) is containing Co metal hydrate, or Ni (OH)
2, H
0.66(NiO
2) (H
2o)
0.91the nickeliferous metal hydrate of series.When m value is 0, it is corresponding metal hydroxides or its hydrate, and when m value is greater than 0, when n value is 0, it is for being similar to H
0.66(NiO
2) (H
2o)
0.91deng compound, when q value is 0, it is for being similar to the compound of FeO (OH).
Preferably, in described general formula, m is 0, n be not 0, q value is 0 ~ 6.
Preferably, in described general formula m be not 0, n different with q value time be 0, q value be 0 ~ 6.
Preferably, described many metal hydrates are the compound [Ax with following general formula ... By] Om (OH) n (H
2o) compound of q or its hydrate, described general formula comprises two or more metallic elements, these metallic elements are independently selected from chromium, cobalt, nickel, molybdenum, manganese, copper, tin, titanium, cadmium, vanadium, lithium, sodium, potassium, zinc and iron, are 0 when in formula, n, m are different with q.
Preferred, described many metal hydrates are compd A xByOm (OH) n (H with following general formula
2o) compound of q or its hydrate, described metal element A is chromium, cobalt, nickel, molybdenum, manganese, copper, tin, titanium, cadmium or vanadium, B be metal as, Na, K, Zn, Cu, Li or Fe.In formula x and y value be greater than 0, n different with q time be 0.When n value is 0, it is corresponding oxometallate, such as Li
0.1 – 2mn
1 – 2o
3-4compounds, its performance is better than monometallic composite oxides under normal circumstances.
In described general formula, AxBy is the metallic element contained in element, and those skilled in the art can know, and these two general formulas and aforesaid metal hydrate should meet the requirement of Coordinative Chemistry and valence state simultaneously.Metal ion in general formula be relate in male or female oxide material chromium, iron, cobalt, nickel, molybdenum, manganese, copper, tin, titanium, cadmium, vanadium and silicon, the corresponding oxidation state of boron and phosphorus or reduction-state, such as manganese ion, have Mn
3+, Mn
4+.It all may be used for preparation of the present invention.
Preferably, in described general formula, m is 0, n be not 0, q value is 0 ~ 6.
Preferably, in described general formula m be not 0, n different with q value time be 0, q value be 0 ~ 6.
Preferably, described nonmetal oxide is compound MOm (OH) n (H with following general formula
2o) when q, M are nonmetalloid, can be B, C, Si, P etc., be 0 when in formula, n with q is different.
Preferably, the granularity of described nonmetal oxide, metal oxide or poly-metal deoxide is relevant to n and q number in compound formula, and this number is larger, and the solid particle hole obtained is many, and specific surface is larger.
In an embodiment of the present invention, the preparation method of described Graphene is as follows:
Adopt classical Hummers legal system for graphite oxide, get 1 g high-purity natural crystalline flake graphite, 1 g sodium nitrate adds in the 50 ml concentrated sulfuric acids, uniform stirring 4h in ice bath, makes graphite exhaustive oxidation, then slowly add 6g potassium permanganate wherein, under remaining on 30 DEG C of temperature, add thermal agitation 4 hours.Slowly add 80 ml deionized waters wherein, bath temperature be elevated to 90 DEG C and continue heating 2 hours.Add 200 ml deionized waters after completion of the reaction, and with syringe by 6 ml H
2o
2dropwise join in reaction solution, in and the complete potassium permanganate of unreacted, now the color of solution becomes golden yellow by pitchy.
Its post-processing step is as follows:
The golden solution of preparation is carried out vacuum filtration, and filter cake good for suction filtration is dissolved in deionized water again, then stir until graphite oxide dissolves formation graphite oxide solution again, carried out high speed centrifugation, and wash with water and ethanol respectively, then vacuumize is carried out to it and namely obtain graphite oxide.Again graphite oxide ultrasonic disperse in distilled water is obtained graphene oxide solution.
Aforementioned oxidation Graphene also can adopt other method to prepare.
Preferably, the temperature of hydro-thermal reaction is 120-300 DEG C.
Preferably, the concentration of described graphene oxide is 0.2 ~ 4 mg/mL.
Preferably, the suspension-turbid liquid of described metal hydrate and/or many metal hydrates or the concentration of solution are 0.1-10g/mL.
Preferably, the concentration of described nonmetal hydrate is 0.1-2g/mL.
Preferably, the described hydro-thermal reaction time is 5 ~ 30h.
Preferably, described method also comprises: while hydro-thermal reaction, is placed in by electrode current collecting body in reaction system, takes out electrode after reacting completely, obtain combination electrode material, and described current collector body material is Ni net, Cu or graphite etc.
Method of the present invention is simple, and pollution-free, performance is good, overcomes that the capacity that positive electrode that conventional method obtains exists is lower, the not high defect of cyclical stability.The composite material that the present invention prepares is layer structure, and technique is simple, and power consumption is few, and after composite graphite alkene, conductance is high, and capacity is high, good cycle, has potential industrial production and is worth.
Accompanying drawing explanation
The XRD figure of Fig. 1, lithium manganese oxide/graphene combination electrode material.
The SEM figure of Fig. 2, lithium manganese oxide/graphene combination electrode material.
Cyclic voltammogram after Fig. 3, lithium manganese oxide/graphene combination electrode material discharge and recharge the 1st time and 200 times.
Embodiment
The following is the embodiment of the application, it is only used as the explanation of the application and unrestricted.
Embodiment 1, the present embodiment are the combination electrode material that raw material has prepared containing metal FeO-Graphene with FeO (OH) and graphene oxide.
The preparation method of described graphene oxide solution is as follows:
Adopt classical Hummers legal system for graphite oxide, get 1 g high-purity natural crystalline flake graphite, 1 g sodium nitrate adds in the 50 ml concentrated sulfuric acids, stir in ice bath be stirred to uniformly blackish green.Then slowly add 6g potassium permanganate wherein, under remaining on 30 DEG C of temperature, add thermal agitation 4 hours.Slowly add 80 ml deionized waters wherein, bath temperature be elevated to 90 DEG C and continue heating 2 hours.Add 200 ml deionized waters after completion of the reaction, and with syringe by 6 ml H
2o
2dropwise join in reaction solution, in and the complete potassium permanganate of unreacted, now the color of solution becomes golden yellow by pitchy.
Its post-processing step is as follows:
The golden solution of preparation is carried out vacuum filtration, and filter cake good for suction filtration is dissolved in deionized water again, then stir until graphite oxide dissolves formation graphite oxide solution again, then high speed centrifugation is carried out, and wash with water and ethanol respectively, then vacuumize is carried out to it and namely obtain graphite oxide.Again graphite oxide ultrasonic disperse in distilled water is obtained graphene oxide solution.
The FeO (OH) of 4.45g is scattered in water the system obtaining concentration 0.09 g/ml, and to get liquid 3mL and concentration be that the Graphene 10mL of 0.5 mg/mL fully mixes, move in hydrothermal reaction kettle, naturally cool after keeping 180 degrees Celsius of lower hydro-thermal reaction 15h, remove supernatant liquor naturally to dry, obtain combination electrode material.This combination electrode material is layer structure, and is Nano grade.
In the preparation process of electrode composite material, also can be placed in reaction system by electrode current collecting body, take out electrode, obtain combination electrode after reacting completely, described electrode current collecting body is Ni net, Cu or graphite material etc.
The battery material capacity that this embodiment prepares is 476F/g.Inventor has also selected different raw material ratio to test, and for verifying feasibility of the present invention, its actual conditions is see table 1:
Table 1: the reaction condition of embodiment 2 ~ 9
Embodiment 10, the present embodiment are with nonmetal hydrate Ludox N
b/ N
siO3when being respectively 1 and 2, being that the combination electrode material containing nonmetal oxide-Graphene prepared by raw material with graphene oxide in LiOH medium, can finding out that from its SEM figure it is Nano grade.
The preparation method of this embodiment Graphene is with embodiment 1, and its difference is only to add N
b/ N
siO3than the Ludox 5mL being 2, all the other conditions, with embodiment 1, have finally obtained containing the nonmetal oxide of Si, B and the combination electrode material of Graphene.The first capacity of the battery material that this embodiment prepares in non-aqueous electrolytic solution is 865 mAh/g.
Inventor has also selected different raw materials to carry out experiment under different condition for verifying feasibility of the present invention, and its actual conditions is see table 2:
Table 2: the reaction condition of embodiment 11 ~ 18
Embodiment 19, the present embodiment are with Li
0.1 – 2mn
1 – 2o
3-4be the combination electrode material that the oxide/Graphene containing metal Li-Mn prepared by raw material with graphene oxide.
The preparation method of this embodiment Graphene is with embodiment 1, and its difference is only to add the LiMnO that concentration is 1g/mL
4(H
2o)
32mL, all the other conditions, with embodiment 1, have finally obtained containing LiMnO
4-and the electrode composite material of Graphene, the XRD figure of this electrode composite material is shown in Fig. 1, electrode composite material SEM figure see Fig. 2, can find out that from Fig. 1 and Fig. 2 the degree of crystallinity after compound is better, homogenize material.The battery material capacity 487F/g that this embodiment prepares.
Fig. 3 be electrode composite material cyclic voltammogram, as can be seen from the figure: after the cyclic voltammetric after 200 times, capacity only loses 13%.
Inventor has also selected different raw materials to carry out experiment under different condition for verifying feasibility of the present invention, and its actual conditions is see table 3:
Table 3: the reaction condition of embodiment 20 ~ 25
Embodiment 26, the present embodiment are with LiMnO
4(H
2o)
3be the combination electrode material that the oxide/Graphene containing metal Li-Mn prepared by raw material with graphene oxide.
The preparation method of this embodiment Graphene is with embodiment 19, and its difference is only to add the silicic acid 2mL that concentration is 1g/mL, and all the other conditions, with embodiment 1, have finally obtained the electrode composite material containing lithium manganese oxide, nonmetal silicon and Graphene.The battery material capacity that this embodiment prepares is 501 F/g.
Inventor has also selected different raw materials to carry out experiment under different condition for verifying feasibility of the present invention, and its actual conditions is see table 4:
The reaction condition of table 4: embodiment 27-33
Aforesaid embodiment is metal hydrate or many metal hydrates and graphene oxide hydro-thermal reaction and prepares combination electrode material, if metal hydrate, many metal hydrates and graphene oxide hydro-thermal reaction also can be prepared the electrode material of poly-metal deoxide and Graphene compound;
Inventor has also carried out calcination processing to the part combination electrode material that embodiment 1-33 obtains, the temperature of calcination processing be 100-800 degree Celsius not etc., its performance all increases, and table 5 is corresponding embodiment calcination condition.
Table 5, calcining heat-treat condition
Claims (10)
1. the preparation method of metal/non-metal oxide/Graphene or poly-metal deoxide/graphene combination electrode material, comprising:
By the suspension-turbid liquid of metal hydrate and/or many metal hydrates or solution and graphene oxide solution according to volume ratio 1-5:0.05-1, or after the suspension-turbid liquid of the hydrate of nonmetal oxide or solution mixes according to the volume ratio of 1-5:0.05 ~ 1 with graphene oxide solution respectively, hydro-thermal reaction a few hours at 100-300 DEG C.
2. method according to claim 1, is characterized in that, described method also comprises further:
After the product separation liquid phase of hydro-thermal reaction, the solid phase obtained, in 100 ~ 800 DEG C of calcination activations, obtains containing metal oxide or poly-metal deoxide/graphene combination electrode material.
3. method according to claim 1 and 2, is characterized in that, described metal hydrate is compd A Om (OH) n (H with following general formula
2o) q, described metallic element comprises chromium, iron, cobalt, nickel, molybdenum, manganese, copper, tin, titanium, cadmium or vanadium, is 0 when in formula, n with q is different;
Described many metal hydrates are the compound [Ax with following general formula ... By] Om (OH) n (H
2o) compound of q or its hydrate, described general formula comprises two or more metallic elements, these metallic elements are independently selected from chromium, cobalt, nickel, molybdenum, manganese, copper, tin, titanium, cadmium, vanadium, lithium, sodium, potassium, zinc and iron, are 0 when in formula, n, m are different with q.
4. method according to claim 3, is characterized in that, described many metal hydrates are for having following general formula AxByOm (OH) n (H
2o) compound of q or its hydrate, described metal element A is chromium, cobalt, nickel, molybdenum, manganese, copper, tin, titanium, cadmium or vanadium, and B is metal Na, K, Zn, Cu, Li or Fe.
5. method according to claim 1 and 2, is characterized in that, described nonmetal oxide is compound MOm (OH) n (H with following general formula
2o) q, in formula, M is nonmetalloid, and described nonmetalloid M is B, C, Si or P, is 0 when in formula, n with q is different.
6. method according to claim 1 and 2, it is characterized in that, described method also comprises: while hydro-thermal reaction, electrode current collecting body is placed in reaction system, electrode and attachment thereof is taken out after reacting completely, oven dry obtains combination electrode, and described electrode material is metal oxide/Graphene or poly-metal deoxide/graphene complex.
7. method according to claim 1 and 2, is characterized in that, the temperature of hydro-thermal reaction is 120 ~ 300 DEG C.
8. method according to claim 1 and 2, is characterized in that, the concentration of described graphene oxide is 0.2 ~ 4mg/mL.
9. method according to claim 1 and 2, is characterized in that, the suspension-turbid liquid of described metal hydrate or many metal hydrates or the concentration of solution are 0.2 ~ 10g/mL.
10. method according to claim 1 and 2, is characterized in that, the described hydro-thermal reaction time is 5 ~ 30h.
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| CN105789604A (en) * | 2016-04-19 | 2016-07-20 | 陕西科技大学 | Self-knitting nanometer strip-shaped molybdenum trioxide flexible electrode material and preparing method thereof |
| CN105938761A (en) * | 2016-03-21 | 2016-09-14 | 浙江大学 | Magnesium-cobalt oxide/graphene composite material used as supercapacitor electrode material and preparation method thereof |
| CN107394165A (en) * | 2017-07-25 | 2017-11-24 | 南京红太阳新能源有限公司 | A kind of Preparation equipment and method of graphene tin cobalt lithium cell cathode material |
| CN107706003A (en) * | 2017-08-31 | 2018-02-16 | 景德镇陶瓷大学 | A kind of hydro-thermal method prepares graphene/CaTi2O4(OH)2The method of composite granule and its obtained product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105938761A (en) * | 2016-03-21 | 2016-09-14 | 浙江大学 | Magnesium-cobalt oxide/graphene composite material used as supercapacitor electrode material and preparation method thereof |
| CN105789604A (en) * | 2016-04-19 | 2016-07-20 | 陕西科技大学 | Self-knitting nanometer strip-shaped molybdenum trioxide flexible electrode material and preparing method thereof |
| CN105789604B (en) * | 2016-04-19 | 2018-08-31 | 陕西科技大学 | It is a kind of to weave nano strip molybdenum trioxide flexible electrode material and preparation method thereof certainly |
| CN107394165A (en) * | 2017-07-25 | 2017-11-24 | 南京红太阳新能源有限公司 | A kind of Preparation equipment and method of graphene tin cobalt lithium cell cathode material |
| CN107706003A (en) * | 2017-08-31 | 2018-02-16 | 景德镇陶瓷大学 | A kind of hydro-thermal method prepares graphene/CaTi2O4(OH)2The method of composite granule and its obtained product |
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