CN105800597A - Method for preparing mechanically peeled high-conductivity composite graphene - Google Patents
Method for preparing mechanically peeled high-conductivity composite graphene Download PDFInfo
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- CN105800597A CN105800597A CN201610106146.3A CN201610106146A CN105800597A CN 105800597 A CN105800597 A CN 105800597A CN 201610106146 A CN201610106146 A CN 201610106146A CN 105800597 A CN105800597 A CN 105800597A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
The invention discloses a method for preparing mechanically peeled high-conductivity composite graphene. The method comprises the following steps: by taking graphite as a raw material, firstly, permeating metallic ions into graphitic layers, heating the composite graphite so as to enable metal halide and organic acid or an organic acid solution to react so as to obtain organic acid metallic salt, decomposing the organic acid metallic salt so as to obtain metallic oxide, by virtue of the characteristic that the carbon element has the reduction property, reducing the metallic oxide in situ so as to obtain metallic nanoparticles, and performing mechanical peeling, thereby obtaining the high-conductivity composite graphene. According to the method, the graphite is directly used as the raw material, the metal is permeated into the graphitic layers in an ionic state, the electrophilic effect of the pi bonds of the graphitic layers is utilized, the problem that metallic particles in the graphitic layers are not uniformly distributed as the metal halide is directly decomposed at high temperature is overcome, use of high-activity alkali metal is avoided, and the whole process is safe and reliable, low in cost, environment-friendly and applicable to large-scale production.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, particularly to the preparation method of a kind of mechanical stripping high conductivity composite graphite alkene.
Background technology
The advantage such as Graphene has intrinsic mobility height, specific surface area is big, Young's modulus is high and fracture strength is big, is the ideal chose of conducting host materials in lithium ion battery, ultracapacitor.Graphene is the good conductor of electronics, it is possible to build conductive network for electrode material；The specific surface area of its superelevation can dispersive electrode material, it is prevented that the reunion of nano-particle.But Graphene there is also the problem that impedance is higher at present, strongly limit its application in association area.Conventional method is the good electric conductivity of metal material can be utilized to carry out the defect of crane span structure graphene film by the compound of Graphene Yu metal, thus the conductive characteristic of graphene film is substantially improved.
The preparation method that China Patent Publication No. 101051542 discloses a kind of graphite base high conductive composite powder material, it is characterised in that comprise the following steps: 1) precursor power: metal chloride is inserted in expanded graphite layer and be prepared into metal chloride-expanded graphite interlayer compound；2) washing is dry: with distilled water or alcohol solvent by the residual chlorine compound washes clean in metal chloride-expanded graphite intercalation compound presoma, obtain the presoma of clean dry；3) roasting: by the presoma of clean dry and roasting under high temperature 2-4 hour；4) it is quenched: put into immediately after product of roasting is taken out in the distilled water under room temperature and be quenched；5) post processing: quenched product is filtered, dries, then pulverize, obtain product.The composite powder material that the method obtains has that cost is low, conductivity is high and Organic substance has the feature of the good compatibility.But, in Instructions Page 2, introduce those skilled in the art in implementing program process, find the distribution in " farmland shape " of the chloride in the presoma utilizing molten-salt growth method to prepare, and then the metal-oxide also distribution in " farmland shape " that water and chloride are obtained by reacting, it can thus be appreciated that, adopt molten-salt growth method to utilize metal chloride to insert as graphite layers and occur that insert is reunited serious when body prepares graphite-based high conductivity composite powder material, reduction not easily problem thoroughly.
In prior art, the preparation method that China Patent Publication No. 102807845A discloses the high heat conduction and heat radiation material that a kind of thin graphene interlayer comprises metallic particles, step A, the hydrogen peroxide mixing that graphite adopts concentration be 30%-60%, add the oleum containing 20% sulfur trioxide or 96% concentrated sulphuric acid and phosphorus pentoxide, prepare sulphuric acid intercalated graphite, wash and dry；Step B, microwave, obtain the thin graphene expanded, ultrasonic cleavage, dry；Step C, step A and step B one or many circulates, and makes the Graphene number of plies 2-50 layer prepared, lamella size 2-300 micron, carbon-to-oxygen ratio 20-100；Step D, intercalation metal chloride or metal simple-substance；Step E, by the thin graphene containing metal chloride intercalation of preparation in step D, adopts hydrogen reducing.Metallic particles original position is saved in thin graphene between layers by the present invention, improves the thermal conductance of Z-direction, and environmental pollution is little, and cost is low, is suitable for industrialized mass production.But, the method adopts microwave means to obtain expanded graphite, it is impossible to be applied to the large-scale production of electrode material, and operating process is complicated, and environment is also resulted in electromagnetic pollution.
The preparation method that China Patent Publication No. 104694989A discloses a kind of graphene-based metallic composite, first the working electrode in using graphene aerogel as three-electrode system, the method adopting electro-deposition, obtain graphene-based metal composite pre-product, then, the graphene-based metal composite pre-product obtained is then through being thermally treated resulting in graphene-based metallic composite.Due to the method adopting electro-deposition so that the preparation method of graphene-based metallic composite provided by the invention is not related to any high energy consumption high pollution operation, and environment friendly is strong.But the resistance of the method acquisition composite graphite alkene is still significantly high is 10～100 Ω, and adopts precious metals pt as electrode, and raw material is graphene aerogel, cost intensive.
Visible, prior art makes graphite layers insert be uniformly dispersed but without one, and safe operation process is reliable, with low cost, the technological means being suitable for large-scale production prepares Graphene and metallic composite.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, directly adopt graphite as raw material, first metal ion is penetrated into graphite layers, metal halide and organic acid or acylate is made to react acquisition metal salts of organic acids by the method that composite graphite is heated, make metal salts of organic acids decompose and obtain metal-oxide, then carbon is utilized to have the feature of reduction characteristic, metal-oxide original position is made to be reduced, obtain metal nanoparticle, adopt mechanical stripping to be obtained with high conductivity composite graphite alkene afterwards again.The method directly uses graphite as raw material, and cost is greatly reduced, and is suitable for serialization industrial manufacture process, and the compatible technique of mechanical stripping Graphene, the company being suitable for the existing basis of part directly goes into operation.
The preparation method that the present invention provides a kind of mechanical stripping high conductivity composite graphite alkene, said method comprising the steps of:
A. providing electrolyte solution, described electrolyte solution is that electrolyte metal halogen is dissolved in the electrolyte solution that solvent orange 2 A is formed；
B. provide graphite material as raw material, described raw material is thrown in described electrolyte solution, described raw material is 10 ~ 200mg/L in the concentration of electrolyte solution, stand 1 ~ 5 day, the metal ion in electrolyte solution is made jointly to penetrate into described graphite material interlayer with described solvent orange 2 A, form intercalated graphite, separate and take out intercalated graphite；
C. when passing into protective gas, described intercalated graphite is warming up to 700～900 DEG C, reacts 0.5～1h; after making described metal halide react with solvent orange 2 A; decompose and obtain metal-oxide and gas, increase graphite layers distance, after cooling, obtain metal-oxide intercalated graphite；
D. when passing into protective gas; described metal-oxide intercalated graphite is warming up to 900～1500 DEG C, reacts 0.5～1h, make metal-oxide by described graphite in-situ reducing; obtain metal intercalation graphite after cooling, then carry out mechanical stripping and obtain metallic graphite carbon alkene composite.
Preferably, described halogen is at least one in lithium halide, magnesium halide, calcium halide, iron halide, copper halide, aluminum halide, nickel halogenide, zinc halide, silver halide, and described halogen concentration in a solvent is 30 ~ 700mg/L.
Preferably, described graphite material is compact crystal shape graphite, one or more in crystalline flake graphite, expanded graphite or expansible graphite.
Preferably, described solvent orange 2 A is the aqueous solution of organic acid or acylate, concentration is 10 ~ 100mg/L, described organic acid or salt are 1-ethyl-3-methylimidazole Tetrafluoroboric acid, 1-ethyl-3-methylimidazole five acetyl fluoride imines, 1-ethyl-3-methylimidazole two cyaniding nitrogen, 1-ethyl-3,5-methylimidazole fluoroform sulfimide, 1, one or more in 3-diethyl-4-methylimidazole fluoroform sulfimide or 1,3-diethyl-5-Methylimidazole. fluoroform sulphonyl.
Preferably, described mechanical stripping is the one during air-flow stripping, mechanical shock stripping or screw extruding are peeled off.
Preferably, the resistivity of described metallic graphite carbon alkene composite is 10-7~10-8Ω·cm。
Said one in the embodiment of the present application or multiple technical scheme, at least have one or more technique effects following:
1, the program mainly utilizes organic acid or acylate and metal halide as reactant, react under the high temperature conditions, obtain metal salts of organic acids, and metal salts of organic acids is obtaining metal-oxide and gas through pyrolytic, the gas generated expands graphite layers distance, improve metal oxide dispersion uniformity, the metal nanoparticle that after being more beneficial for, metal oxide back obtains is evenly distributed at graphenic surface.
2, adopt organic acid or acylate solution to make use of organic acid or salt without the feature of strong oxidizing property as solvent and reactant in the program, organic acid can dissociate entrance graphite layers and metal ion slow reaction, it is to avoid the strong oxidation to graphite.
3, the program adopts original position graphite reduction metal-oxide to obtain nano-metal particle, reduces the use of other raw materials, reduces cost, environmental protection, applicable large-scale production.
Detailed description of the invention
By detailed description of the invention, the present invention is described in further detail, but this should not being interpreted as, the scope of the present invention is only limitted to Examples below.When without departing from said method thought of the present invention, the various replacements made according to ordinary skill knowledge and customary means or change, should be included in the scope of the present invention.
Embodiment one
500g expanded graphite is thrown in LiF be dissolved in the 1-ethyl-3-methylimidazole Tetrafluoroboric acid that concentration is 10mg/L in the electrolyte solution that formation concentration is 30mg/L, stir, expanded graphite concentration in electrolyte solution is 20mg/L, after standing 1 day, metal-lithium ion in electrolyte solution and 1-ethyl-3-methylimidazole Tetrafluoroboric acid penetrate into expanded graphite interlayer jointly, form intercalated graphite, then, take out the expanded graphite of intercalation, 700 DEG C it are warming up to when passing into Ar gas, through 0.5h, LiF and 1-ethyl-3-methylimidazole Tetrafluoroboric acid reacts, obtain LiBF4, and at high temperature resolve into lithium oxide and gas CO2、N2And HF, the generation of gas adds graphite layers distance, and graphite expands, and obtains lithium oxide intercalated graphite after cooling.Next; when Ar atmosphere protection; lithium oxide intercalated graphite is warming up to 900 DEG C; through 0.5h; the lithium oxide of graphite layers is by graphite in-situ reducing; obtain metal Li intercalated graphite after cooling, then peel off with screw extruding and obtain metallic graphite carbon alkene composite, it is thus achieved that metallic graphite carbon alkene composite powder.The resistivity of the metallic graphite carbon alkene composite obtained in embodiment one is 8.2 × 10-8Ω·cm。
Embodiment two
500g expanded graphite is thrown in LiF be dissolved in the 1-ethyl-3-methylimidazole Tetrafluoroboric acid that concentration is 10mg/L in the electrolyte solution that formation concentration is 500mg/L, stir, expanded graphite concentration in electrolyte solution is 200mg/L, after standing 3 days, metal-lithium ion in electrolyte solution and 1-ethyl-3-methylimidazole Tetrafluoroboric acid penetrate into expanded graphite interlayer jointly, form intercalated graphite, then, take out the expanded graphite of intercalation, 800 DEG C it are warming up to when passing into Ar gas, through 0.5h, LiF and 1-ethyl-3-methylimidazole Tetrafluoroboric acid reacts, obtain LiBF4, and at high temperature resolve into lithium oxide and gas CO2、N2And HF, the generation of gas adds graphite layers distance, and graphite expands, and obtains lithium oxide intercalated graphite after cooling.Next; when Ar atmosphere protection; lithium oxide intercalated graphite is warming up to 900 DEG C; through 0.5h; the lithium oxide of graphite layers is by graphite in-situ reducing; obtain metal Li intercalated graphite after cooling, then peel off with screw extruding and obtain metallic graphite carbon alkene composite, it is thus achieved that metallic graphite carbon alkene composite powder.The resistivity of the metallic graphite carbon alkene composite obtained in embodiment two is 9.1 × 10-8Ω·cm。
Embodiment three
500g expanded graphite is thrown in into MgF2Be dissolved in the 1-ethyl-3-methylimidazole five acetyl fluoride imide liquor that concentration is 100mg/L in the electrolyte solution that formation concentration is 30mg/L, stir, expanded graphite concentration in electrolyte solution is 20mg/L, after standing 1 day, and the metal ions M g in electrolyte solution2+Jointly penetrate into expanded graphite interlayer with 1-ethyl-3-methylimidazole five acetyl fluoride imide liquor, form intercalated graphite, then, take out intercalated graphite and be warming up to 800 DEG C when passing into Ar gas, through 0.5h, MgF2With 1-ethyl-3-methylimidazole five acetyl fluoride imine reaction, it is thus achieved that five acetyl fluoride imines magnesium, resolve into magnesium oxide and gas, gas CO under the high temperature conditions2、N2Generation with HF adds graphite layers distance, and graphite expands, and obtains magnesium oxide intercalated graphite after cooling.Next; when Ar atmosphere protection; magnesium oxide intercalated graphite is warming up to 1000 DEG C; through 0.5h; magnesium oxide is by the carbon in-situ reducing in graphite; obtain metal Mg intercalated graphite after cooling, then peel off with mechanical shock and obtain metallic graphite carbon alkene composite, it is thus achieved that metallic graphite carbon alkene composite powder.The resistivity of the metallic graphite carbon alkene composite obtained in embodiment three is 1.5 × 10-7Ω·cm。
Embodiment four
500g crystalline flake graphite is thrown in into FeCl3Being dissolved in 1, the 3-diethyl-5-Methylimidazole. fluoroform sulphonyl that concentration is 10mg/L in the electrolyte solution formed, stir, expanded graphite concentration in electrolyte solution is 20mg/L, after standing 1 day, and the metal cations Fe in electrolyte solution3+Jointly penetrate into expanded graphite interlayer with 1,3-diethyl-5-Methylimidazole. fluoroform sulphonyl, form intercalated graphite, then, take out intercalated graphite and be warming up to 900 DEG C when passing into Ar gas, through 0.8h, Fe3+React with 1,3-diethyl-5-Methylimidazole. fluoroform sulphonyl, it is thus achieved that trifluoromethanesulfonic acid ferrum, and pyrolytic becomes metal Fe2O3With gas CO2、N2And HF, gas CO2、N2Generation with HF adds graphite layers distance, and graphite expands, and obtains Fe after cooling2O3Intercalated graphite.It follows that when Ar atmosphere protection, by Fe2O3Intercalated graphite is warming up to 1200 DEG C, through 0.8h, Fe2O3By the carbon in-situ reducing in graphite, obtaining metal Fe intercalated graphite after cooling, then peel off with screw extruding and obtain metallic graphite carbon alkene composite, the resistivity of the metallic graphite carbon alkene composite obtained in embodiment four is 2.6 × 10-7Ω·cm。
Embodiment five
500g crystalline flake graphite is thrown in into AlCl3Being dissolved in 1, the 3-diethyl-5-Methylimidazole. fluoroform sulphonyl that concentration is 10mg/L in the electrolyte solution formed, stir, expanded graphite concentration in electrolyte solution is 20mg/L, after standing 1 day, and the metal ion Al in electrolyte solution3+Jointly penetrate into expanded graphite interlayer with 1,3-diethyl-5-Methylimidazole. fluoroform sulphonyl, form intercalated graphite, then, take out intercalated graphite and be warming up to 900 DEG C when passing into Ar gas, through 0.5h, Al3+React with 1,3-diethyl-5-Methylimidazole. fluoroform sulphonyl, it is thus achieved that trifluoromethanesulfonic acid ferrum, and pyrolytic becomes metal Al2O3With gas CO2、N2And HF, gas CO2、N2Generation with HF adds graphite layers distance, and graphite expands, and obtains Al after cooling2O3Intercalated graphite.It follows that when Ar atmosphere protection, metal-oxide intercalated graphite is warming up to 900 DEG C, through 0.5h, Al2O3By the carbon in-situ reducing in graphite, obtaining metal Al intercalated graphite after cooling, then peel off with screw extruding and obtain metallic graphite carbon alkene composite, the resistivity of the metallic graphite carbon alkene composite obtained in embodiment five is 4.5 × 10-7Ω·cm。
Embodiment six
500g crystalline flake graphite is thrown in into CuCl2Being dissolved in 1, the 3-diethyl-5-Methylimidazole. fluoroform sulphonyl that concentration is 10mg/L in the electrolyte solution formed, stir, expanded graphite concentration in electrolyte solution is 20mg/L, after standing 5 days, and the metal ion Cu in electrolyte solution2+Jointly penetrate into expanded graphite interlayer with 1,3-diethyl-5-Methylimidazole. fluoroform sulphonyl, form intercalated graphite, then, take out intercalated graphite and be warming up to 900 DEG C when passing into Ar gas, through 0.5h, Cu2+React with 1,3-diethyl-5-Methylimidazole. fluoroform sulphonyl, it is thus achieved that trifluoromethanesulfonic acid ferrum, and pyrolytic becomes Ni metal O and gas CO2、N2And HF, gas CO2、N2Generation with HF adds graphite layers distance, and graphite expands, and obtains CuO intercalated graphite after cooling.Next; when Ar atmosphere protection; metal-oxide intercalated graphite is warming up to 1500 DEG C; through 0.5h; CuO is by the carbon in-situ reducing in graphite; obtaining Ni metal intercalated graphite after cooling, then peel off with screw extruding and obtain metallic graphite carbon alkene composite, the resistivity of the metallic graphite carbon alkene composite obtained in embodiment six is 7.5 × 10-8Ω·cm。
Although preferred embodiments of the present invention have been described, but those skilled in the art are once know basic creative concept, then these embodiments can be made other change and amendment.So, claims are intended to be construed to include preferred embodiment and fall into all changes and the amendment of the scope of the invention.
Obviously, the present invention can be carried out various change and modification without deviating from the spirit and scope of the present invention by those skilled in the art.So, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.
Claims (6)
1. the preparation method of a mechanical stripping high conductivity composite graphite alkene, it is characterised in that said method comprising the steps of:
A. providing electrolyte solution, described electrolyte solution is that electrolyte metal halogen is dissolved in the electrolyte solution that solvent orange 2 A is formed, and described solvent orange 2 A is the aqueous solution of organic acid or acylate；
B. provide graphite material as raw material, described raw material is thrown in described electrolyte solution, described raw material is 10 ~ 200mg/L in the concentration of electrolyte solution, stand 1 ~ 5 day, the metal ion in electrolyte solution is made jointly to penetrate into described graphite material interlayer with described solvent orange 2 A, form intercalated graphite, separate and take out intercalated graphite；
C. when passing into protective gas, described intercalated graphite is warming up to 700～900 DEG C, reacts 0.5～1h; after making described metal halide react with solvent orange 2 A; decompose and obtain metal-oxide and gas, increase graphite layers distance, after cooling, obtain metal-oxide intercalated graphite；
D. when passing into protective gas; described metal-oxide intercalated graphite is warming up to 900～1500 DEG C, reacts 0.5～1h, make metal-oxide by described graphite in-situ reducing; obtain metal intercalation graphite after cooling, then carry out mechanical stripping and obtain metallic graphite carbon alkene composite.
2. the preparation method of a kind of mechanical stripping high conductivity composite graphite alkene according to claim 1, it is characterized in that, described metal halide is at least one in lithium halide, magnesium halide, calcium halide, iron halide, copper halide, aluminum halide, nickel halogenide, zinc halide, silver halide, and described metal halide concentration in a solvent is 30 ~ 700mg/L.
3. the preparation method of a kind of mechanical stripping high conductivity composite graphite alkene according to claim 1, it is characterised in that described graphite material is compact crystal shape graphite, one or more in crystalline flake graphite, expanded graphite or expansible graphite.
4. the preparation method of a kind of mechanical stripping high conductivity composite graphite alkene according to claim 1, it is characterized in that, the concentration of described solvent orange 2 A is 10 ~ 100mg/L, described organic acid or acylate are 1-ethyl-3-methylimidazole Tetrafluoroboric acid, 1-ethyl-3-methylimidazole five acetyl fluoride imines, 1-ethyl-3-methylimidazole two cyaniding nitrogen, 1-ethyl-3,5-methylimidazole fluoroform sulfimide, 1, one or more in 3-diethyl-4-methylimidazole fluoroform sulfimide or 1,3-diethyl-5-Methylimidazole. fluoroform sulphonyl.
5. the preparation method of a kind of mechanical stripping high conductivity composite graphite alkene according to claim 1, it is characterised in that described mechanical stripping is the one during air-flow stripping, mechanical shock stripping or screw extruding are peeled off.
6. the preparation method of a kind of mechanical stripping high conductivity composite graphite alkene according to claim 1, it is characterised in that the resistivity of described metallic graphite carbon alkene composite is 10-7~10-8Ω·cm。
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Cited By (4)
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| CN108249428A (en) * | 2018-01-23 | 2018-07-06 | 福州大学 | It is a kind of that the method that lithium stripping prepares single-layer graphene is inserted based on electrolyte solvent heat |
| CN110117807A (en) * | 2019-03-09 | 2019-08-13 | 深圳市中科墨磷科技有限公司 | A kind of two-dimensional material-transition metal hetero-junctions preparation of sections method |
| CN114853004A (en) * | 2022-04-25 | 2022-08-05 | 蜂巢能源科技股份有限公司 | Negative electrode material and preparation method and application thereof |
| CN115974059A (en) * | 2022-09-09 | 2023-04-18 | 杭州高烯科技有限公司 | High-elasticity graphene composite aerogel and preparation method and application thereof |
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| CN101051542A (en) * | 2007-03-29 | 2007-10-10 | 武汉工程大学 | Method for preparing graphite base high conductive composite powder material |
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| CN108249428A (en) * | 2018-01-23 | 2018-07-06 | 福州大学 | It is a kind of that the method that lithium stripping prepares single-layer graphene is inserted based on electrolyte solvent heat |
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| CN114853004A (en) * | 2022-04-25 | 2022-08-05 | 蜂巢能源科技股份有限公司 | Negative electrode material and preparation method and application thereof |
| CN115974059A (en) * | 2022-09-09 | 2023-04-18 | 杭州高烯科技有限公司 | High-elasticity graphene composite aerogel and preparation method and application thereof |
| CN115974059B (en) * | 2022-09-09 | 2023-09-05 | 杭州高烯科技有限公司 | High-elastic graphene composite aerogel and preparation method and application thereof |
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