CN103579625A - Carbon-series/active-substance compound and preparation method thereof - Google Patents
Carbon-series/active-substance compound and preparation method thereof Download PDFInfo
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- CN103579625A CN103579625A CN201210257208.2A CN201210257208A CN103579625A CN 103579625 A CN103579625 A CN 103579625A CN 201210257208 A CN201210257208 A CN 201210257208A CN 103579625 A CN103579625 A CN 103579625A
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- 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
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a carbon-series/active-substance compound and a preparation method thereof. The compound comprises: active particles with size of 1-100 nm and one-dimension or two-dimension carbon skeleton which are mutually connected via three-dimension carbon material, and the compound possesses the capability of storing both faraday charges and nonfaraday charges. The addition of multi-dimension carbon allotrope helps to substantially inhibit agglomeration phenomenon of active substances during synthesis and disintegration phenomenon of the active substances during electric charging-discharging, and a multi-dimension conduction network structure after stacking is formed, so that the conductive capability of the material is improved, and further the charging-discharging rate of the material is improved. The invention additionally provides a simple green synthetic method, and thus the carbon-series/active-substance compound possesses batch production potential, and becomes a potential green-energy storage material applicable to lithium ion secondary batteries, super-capacitance lithium-air batteries.
Description
Technical field
The present invention relates to a kind of carbon is activated complex, especially relate to a kind of multidimensional structure high power capacity energy storage material and preparation method thereof, this multidimensional carbon series nanometer grade activated complex, can be in order to manufacture the energy storage device of high-energy-density, particularly lithium rechargeable battery core and to utilize its prepared battery pack.
Background technology
The 21st century coming back in scientific and technological revolution now and environmental consciousness, in response to new science and technology from generation to generation with green can the quick evolution of product, consumer is also synchronizeed growth to the requirement of energy storaging product usefulness and demand.For for example carry-along 3C Product, such as mobile phone, palmtop computer (PDA), intelligent mobile phone (Smart phone), notes type (flat board) computer, digital camera etc., or electric motor car, oily electric hybrid vehicle etc. Large-sized Communication instrument, the capacitance of energy storage device, life-span or even power output etc. require all increasingly harsh, while is because of the new line of environmental consciousness, consumer also throws concern to process of producing product simultaneously, therefore a kind of mass producible Green Chemistry processing procedure is all indispensable for the producer and consumer both sides.Take lithium ion battery as example, and current business-like high energy battery negative pole mostly is graphite, yet its theoretical capacitance only terminates in 372 mAh/g.In order to break through this capacity limit, for the research of emerging negative pole, launch just widely, wherein especially with tin-based material (Sn:998 mAh/g, SnO
2: 780 mAh/g) with the tool development potentiality of both alloy systems of silica-base material (4200 mAh/g).Yet no matter be tinbase or silica-based negative material, its lithium ion entry/leave in charge and discharge process is all accompanied by violent volumetric expansion and contraction, thereby cause alloy material disintegration also significantly to reduce battery cycle life, and become the obstruction of current cathode alloy material maximum in commercialization.
In order to solve and relax the change in volume of cathode alloy material, existing document or patent disclose many kinds of solutions at present.For example U.S. Patent number US 6,143, just openly using metallic salt as predecessor 448 (on April 15th, 1999), via evaporation drying heating and follow-up multiple tracks step, carry out synthesizing porous property high surface area electrode material, and the space staying in advance while synthesizing by porous material holds the volumetric expansion causing after lithium ion is moved into.Yet high specific surface area electrode material is also incorrect for some electrochemical applications, lithium ion secondary battery negative pole particularly, if using metallic salts such as chlorate, sulfate as predecessor, to make atom utilization (atom utilization) only only have 40% to 60%, this and Green Chemistry concept run in the opposite direction.
U.S. Patent number US 6,103, openly produce nanocarbon/metal composite particles material with aeroge synthetic method 393 (on Augusts 27th, 1998), this processing procedure is used commercialization porous carbon as base material, and after absorbing metallic salt predecessor, with ejection processing procedure, make metal solvent be embedded in carbon material more inner, the carbon material system in this example is mainly as carrier
,carried metal has platinum, silver, palladium, ruthenium, osmium etc., and is applicable to the electrochemical catalyst reaction of for example application of fuel cell.Because case is before this to using metallic salts such as chlorate, sulfate as predecessor, will makes equally atom utilization (atom utilization) only only have 40% to 60%, and run in the opposite direction with Green Chemistry concept.
U.S. Patent number US 7,094, disclose for 499 (on June 10th, 2003) usings the different carbon material of many moneys (as CNT (carbon nano-tube), carbon fiber, graphite flake etc.) as base material, and in carry out chemical deposition place with metal salt solution, follow-uply re-use the unstable sedimentary deposit that acid solution is come cleaning material surface, thereby make nanocarbon/metal composite material, and this material is carried out to lithium ion battery applications test.But its each material institute tool capacitance is all less than 400 mAh/g.In addition, a large amount of strong acid and metal chloride in this processing procedure, have also been used, the two neither raw material belonging to environment friendliness.
U.S. Patent number US 7,745, disclose for 047 (on November 15th, 2007) and usingd the micron order graphene oxide of chemical stripping 2 ~ 90 percentage by weights as base material, and in modes such as solid-state ball-milling method, chemical vapour sedimentation method or filtration mixed stack, produce various metal/alloy carbon composite electrode, it is comprised of the multiple material such as by alloys various with it such as silicon, germanium, tin, lead, bismuth, aluminium, zinc.Although combination electrode has good electrochemistry performance on lithium rechargeable battery, the synthesis material of the material of this piece of patent must be used a large amount of graphene oxide base materials.In addition, even if utilize the technology of U.S. Patent number US 2,798,878 (on July 19th, 1954) to be still difficult to produce in a large number synthetic graphene oxide, and the use of a large amount of strong oxidizer and strong acid, will cause the not environmental protection of the manufacture process utmost point.If therefore its electrode product will be dropped into volume production, the use amount that reduces graphene oxide is indispensable.
The people such as Zheng M.Y. (Cheng MY, Hwang CL, Pan CJ, Cheng JH, Ye YS, Rick JF and Hwang BJ,
j. Mater. Chem., 2011,21,10705-10710) in 2011, propose to using metallic tin as predecessor with glucose hydro-thermal method assistant, to produce the nanoscale tin ash/carbon composite that can be applied to lithium ion battery anode.This piece of document points out that micron metal tin particle is under glucose participates in, and by oxidized and be reduced to 2～5 nano-scales, and is dispersed evenly to the nanoscale tin ash in parent carbon material.This material can have the capacitance of 521 mAh/g in the application of lithium ion battery; but the dual restriction due to hot carbon reduction temperature and tin metal low melting point; the heat-treatment temperature range of this material is limited in lower than 400 ℃ of following sintering; and the metallic tin grain that hot carbon restores can depart from carbon material and assemble the size for several microns, and electrically fail fast.And only the calcining heat of 400 ℃ to be not sufficient to carbon be matrix carbonization, to cause the conductivity of this material not good, and this carbon is the gathering that matrix cannot effectively suppress reducing activity material, therefore cannot carry out tin ash reduction, also cause the irreversible capacitance of first circle of this material effectively to reduce simultaneously.
Usefulness and its manufacture method of summing up above each electrode material all have its shortcoming.Therefore, how to research and develop the electrode material of the high cycle life of a tool, high power capacity and have both can volume production green processing procedure, will be current energy storage industry very in the urgent need to technology.
This case applicant, in view of deficiency of the prior art, tests and research through concentrated, and the spirit to work with perseverance, and finally visualizes this case, can overcome the deficiency of prior art, is below the brief description of this case.
Summary of the invention
For effectively avoid active material in the gathering of active material in preparation process or charge and discharge process disintegration, promote material electrical conductivity and active material utilance, reduce the irreversible capacitance that the active material material disintegration that volume acute variation causes in charge and discharge process and oxide thereof and high-specific area nano material bring, and minimizing is to the use of the disagreeableness chemical substance of environment and generation of waste materials.The present invention is usingd the particle (as silicon, tin, manganese, iron, cobalt, nickel, copper, germanium, antimony, bismuth, zinc, aluminium, cadmium) of micron order activity and is coordinated carbohydrate (as grape candy, sucrose, lactose, oligosaccharides etc.) as predecessor, through adding zero dimension or one dimension or Two-dimensional Carbon material, and synthesize multidimensional carbon material/nano level active particle composite material by hydro thermal method.
Therefore, the invention provides a kind of carbon is activated complex, comprising: several carbon allotropes; The particle of several tool activity; And the molecular a kind of three-dimensional of several carbohydrates is sticked together carbon material, it is coupled with the particle of those tool activity respectively, so that particle of tool activity is coupled to carbon allotrope described in each described in each, and make described carbon allotrope each other storehouse to become this carbon be activated complex.
Preferably, wherein said carbon allotrope, to be selected from by zero dimension carbon allotrope, one dimension carbon allotrope, Two-dimensional Carbon allotrope and group that wherein two or more combinations forms arbitrarily, wherein this zero dimension carbon allotrope is selected from the group being comprised of nano carbon microsphere, carbon black and activated carbon powder, this one dimension carbon allotrope is selected from the group being comprised of CNT (carbon nano-tube), graphitic carbon pipe and carbon fiber, and this Two-dimensional Carbon allotrope is Graphene or native graphite.
Preferably, wherein in the content of this Two-dimensional Carbon allotrope, account at most the percentage by weight that this carbon is activated complex 5%.
Preferably, this carbon is that this carbon allotrope in activated complex can stem from natural or artificial-synthetic stone's ink sheet, carbon fiber, graphitic carbon pipe, graphitic carbon ball, mesocarbon ball, pitch, petroleum coke, carbon black and crystalline polymer carbon material, to peel off or separation method obtains, thickness or diameter are less than 50 nanometers, and length and width are 1 to 10 micron.
Preferably, the particle of wherein said tool activity is selected from by silicon, tin, manganese, iron, cobalt, nickel, copper, germanium, antimony, bismuth, zinc, aluminium, cadmium metal and group that wherein two or more alloy, oxide, carbide, carbonate, phosphate and complex elements forms arbitrarily.
Preferably, the particle of wherein said tool activity, be embedded in this three-dimensional and stick together the inside of carbon material, or be distributed on the surface of these several carbon allotropes, and the particle of described tool activity has the particle diameter of 1 ~ 100 nanometer, and in being the content of activated complex, this carbon accounts for 20% to 97% percentage by weight.
Preferably, wherein those carbohydrate molecules are the structure with polynary ring, and be to be selected from by single candy, two candy, few candy, polysaccharide and group that wherein two or more combinations forms arbitrarily, this list candy is to be selected from by ribose, deoxyribose, glucose, fructose, galactolipin and group that wherein two or more combinations forms arbitrarily, and this pair of candy is to be selected from by sucrose, lactulose, lactose, maltose and group that wherein two or more combinations forms arbitrarily.
Preferably, this carbon is the particle coupling of these several carbohydrate molecules in activated complex and these several tool activity, make the particle of these several tool activity this several carbon allotropes that are coupled, and with these several carbon allotropes couplings, make these several carbon allotropes storehouse each other.
It is activated complex that the present invention also proposes a kind of carbon, comprising: a conductive materials; The particle of one tool activity; And one carbon be matrix, the particle coupling of itself and this tool activity, so that the particle of this tool activity is coupled to this conductive materials, and makes minimized in size and the stabilisation of the particle of this tool activity.
Preferably, wherein this conductive materials is to be selected from by zero dimension carbon allotrope, one dimension carbon allotrope, Two-dimensional Carbon allotrope, and the group that forms of three-dimensional carbon allotrope, and this carbon is that the precursors of matrix is several carbohydrate molecules.
The present invention also proposes the manufacture method that a kind of nano-scale carbon is activated complex, and it comprises the following step: (a) carbon allotrope, carbohydrate solution are mixed with the particle of micron order tool activity, to form mixed solution; (b) under sealed environment, react this mixed solution, to form an intermediate product; And (c) this intermediate product is calcined, to produce this nano-scale carbon, be activated complex.
Preferably, wherein this step (b) also comprises: (b1) this carbohydrate carbonization being become to carbon is matrix, and by the particle of this micron order tool activity, is oxidized into one and is embedded in the particle that this carbon is the nanoscale tool activity of matrix; This step (c) also comprises: (c1) import a gas, with more than 400 ℃ by the reduction of this intermediate product, wherein this gas is to be selected from by nitrogen, argon gas, carbon monoxide, hydrogen, diamine, lithium, sodium, potassium, magnesium vapor and group that wherein two or more combinations forms arbitrarily.
Preferably, wherein this step (b) is the temperature range at 100 ℃ ~ 350 ℃, and reacts under the pressure limit of 1 bar ~ 150 bar.
Preferably, wherein this step (b) is the temperature range at 150 ℃ ~ 250 ℃, and reacts under the pressure limit of 4 bar ~ 25 bar.
Preferably, in this manufacture method, this carbon is that matrix can be coated on this carbon allotrope top layer by the particle of this nanoscale tool activity
,and make this carbon allotrope form conductive network.
Preferably, in this manufacture method, add this carbon allotrope, can reduce the agglomeration of particle of this tool activity of low melting point.
Preferably, in this manufacture method, add this carbon allotrope, can suppress this composite material in the active material disintegration of charge and discharge process or the growth of material surface passivating film.
Accompanying drawing explanation
Fig. 1 is that carbon of the present invention is sweep electron microscope (SEM) image of activated complex.
Fig. 2 (a) and Fig. 2 (b) are respectively reaction initial schematic diagram and SEM image.
Fig. 3 (a) and Fig. 3 (b) are respectively schematic diagram and the SEM image after hydrothermal treatment consists.
Fig. 4 (a) and Fig. 4 (b) are respectively schematic diagram and the SEM image after reduction calcining.
In Fig. 5: (a) be the X-ray diffraction pattern of metallic tin, tin oxide and tin ash; (b) be composite material X-ray diffraction pattern before calcination process; (c) to (e), be respectively the tin powder X-ray diffraction figure after different time calcining.
Fig. 6 (a) and Fig. 6 (b) are respectively (a) SEM image after 1 hour of calcining and (b) the particle size distribution figure of tin particle.
Fig. 6 (c) and Fig. 6 (d) are respectively (c) SEM image after 4 hours of calcining and (d) the particle size distribution figure of tin particle.
Fig. 7 (a) and Fig. 7 (b) are after (a) hydrothermal treatment consists and the SEM image (b) reducing after calcining.
In Fig. 8: (a) and (b) be respectively (a) manganese carbonate and (b) the X-ray diffraction pattern of the manganese particle of manganese oxide; (c) to (d) be respectively (c) calcining before and (d) calcining after manganese powder x-ray diffraction figure.
Primary clustering symbol description
10 carbon activated complex 20 Graphene tin composite materials
11 three-dimensionals are sticked together carbon material 21 graphene aqueous solution
Dull and stereotyped 22 glucose of 12 Graphenes
13 nano active particle 23 glass puttys.
Embodiment
This case proposed invention can be fully understood by following embodiment explanation, and those of ordinary skills can be completed according to this, yet the embodiment of this case not can be limited by the following example it and implement kenel, those of ordinary skills still can deduce out other embodiment according to the spirit of the disclosed embodiments, and those embodiment all ought belong to scope of the present invention.
Refer to Fig. 1, it is that carbon of the present invention is the sweep electron microscope image of activated complex 10.In Fig. 1, carbon is that activated complex comprises that three-dimensional sticks together carbon material 11, Graphene dull and stereotyped 12 and nano active particle 13.Wherein three-dimensional stick together carbon material 11 can be by by a plurality of Graphene flat boards 12 storehouse each other, also can make average mark be dispersed in three-dimensional and stick together the nano metal active particle 13 in carbon material 11, sticking together on the surface of Graphene flat board 12, is activated complex 10 to form carbon of the present invention.
In the process of hydro thermal method, first micron order active particle can be gradually and glucose solution generation oxidation reaction, and change into nano level active compound particles, thereafter nano level active compound particles can stick together carbon material by three-dimensional, and continue polymerization into about the carbon intermediate product of 200 nanometers, wherein nano active compound particles can be dispersed in carbon intermediate product.After adding graphene oxide, carbon intermediate product can be attached to graphene oxide surface, and binds to array graphene oxide flat board, and presents the micron grade stratiform unique surface form of storehouse again.By this material, after passivity gas is with 400 ℃ ~ 900 ℃ heat treatments, a small amount of hydrogen adding or the carbon of material itself, can be reduced into reactive compound nano active particle, to increase material conductivity, reduces not reciprocal capacity amount of first circle simultaneously.A small amount of graphene oxide adding is played an important role in reactive compound reduction process, it is the agglomeration in the time of can effectively suppressing reactive compound reduction because of graphene oxide, and then reach the unique ability that can control active material particle diameter, moreover larger activated complex, be easier to evenly mix with solution and adhesive agent, and can have preferably tackness when directly coating electrode pad, therefore can increase the cycle life of battery, the last distinctive sp of Graphene
2structure electrical conductivity is key, also can further promote the high speed charging and discharging capabilities of battery.
Embodiment 1
First, by 2.5 grams of graphite (Graphite), 2.5 grams of sodium nitrate (Sodium nitrate, NaNO
3) and 115 milliliters of sulfuric acid (Sulfuric acid, H
2sO
4), in 500 milliliters of ice bath reaction bulbs, evenly mix, and stir with magnetite.Then under agitation slowly add 7.5 grams of potassium permanganate (Potassium Permanganate, KMnO
4) and avoid reaction temperature to surpass 20 ℃.Then reaction bulb is moved to 35 ℃ of water-baths 30 minutes, reacted in backward bottle and slowly added 115 ml deionized water, and reacted 15 minutes after making reaction temperature be warming up to 98 ℃.Follow-up 350 ml deionized water and 23 milliliter of 35% hydrogen peroxide (Hydrogen peroxide, the H of reinjecting
2o
2), and wait for that nature is washed till neutrality by reactant with dialysis water-washing method after cooling, to prepare graphite oxide aqueous solution 21 (as shown in Fig. 2 (a) and 2 (b)).Get the graphite oxide aqueous solution 21 of 10 milliliter of 1 wt%, and add 3.6 grams of glucose 22 (>99.5%; Be preferably D (+) glucose), with magnetite, stir 90 minutes, to allow glucose fully dissolve simultaneously.Follow-uply add 1 gram of micron order glass putty 23 (>99%; Sigma-Aldrich) and stir half an hour.Mixed solution is moved into the reactor of 100 milliliters after its grade is mixed evenly, and (if pressure is 5 bar, temperature is 150 ℃ as 180 ℃ as 10 bar (bar) temperature to take pressure; If pressure is 24 bar, temperature is 220 ℃) under, with oil bath pan continuous heating, stir 5 hours.After question response still is naturally cooling, black powder is taken out with 500 ml deionized water and is rinsed, and in 80 ℃ of baking ovens dried overnight, resulting dried powder is as shown in Fig. 3 (a) and 3 (b).The powder being dried (approximately 2.25 grams) is moved to containing passivity mist (5% H
2 aMP.AMp.Amp 95% Ar) under environment, with 5 ℃ of heating rates per minute, be warming up to 550 ℃, and at 550 ℃, calcine 0 to 4 hour, to obtain the composite material (as shown in Fig. 4 (a) and 4 (b)) of different metal particle size, wherein, this graphene oxide accounts at most 5% percentage by weight of total composite material.
Refer to Fig. 5, by X-ray diffraction analysis instrument (X-ray Diffraction, XRD) collection of illustrative plates, can be determined in the process of calcining, before calcining, in composite material, comprised tin ash (as shown in (b) in Fig. 5).Calcine after 1 hour, in composite material, comprised metallic tin, tin oxide and tin ash, but the content of metallic tin increases, and the content of tin ash reduces (as shown in (c) in Fig. 5).And calcine after 4 hours, in composite material, only there is metallic tin (as shown in (e) in Fig. 5).By above-mentioned experiment, confirmed, nanoscale tin ash crystalline phase system is converted into nano level metal tin phase, and this can significantly reduce the irreversible capacitance of tin ash.
Refer to Fig. 6 (a) ~ 6 (d), it is that above-mentioned composite material is through the result of calcining.At passivity mixed gas (5% H
2 aMP.AMp.Amp 95% Ar), under environment, with 550 ℃ of calcinings, after 1 hour, the average grain diameter of tin particle is 28.73 nm (as shown in Fig. 6 (a) and 6 (b)).And through calcining after 4 hours, the average grain diameter of this tin particle increases to 56.91 nm (as shown in Fig. 6 (c) and 6 (d)).Meanwhile, along with the increase of average grain diameter, and then can there is preferably tackness will make it coat battery lead plate time.
Embodiment 2
In 10 ml deionized water, add 3.6 grams of glucose (>99.5%; Be preferably D (+) glucose), with magnetite, stir and allow glucose fully dissolve in 90 minutes simultaneously, then add 1 gram of micron order glass putty (>99%; Sigma-Aldrich) stir half an hour.After being mixed evenly, by the reactor of 100 milliliters of mixed solution immigrations, the oil bath pan continuous heating that the pressure of take is 180 ℃ as 10 bar (Bar) temperature stirs 5 hours.Deng reactor, black powder is taken out after naturally cooling, then with the deionized water rinsing of 500 milliliters, and in 80 ℃ of baking ovens dried overnight.2.25 grams of powder that have been dried are moved to containing passivity gas (N
2) in, and be controlled at 400 ℃ and calcine 4 hours, to produce nanoscale tin ash carbon composite.
Embodiment 3
In 10 ml deionized water, add 3.6 grams of glucose (>99.5%; Be preferably D (+) glucose), simultaneously with magnetite, stir and allow glucose fully dissolve in 90 minutes, follow-uply add 1 gram of micron order glass putty (>99%; Sigma-Aldrich) stir half an hour.After being mixed evenly, by the reactor of 100 milliliters of mixed liquor immigrations, the oil bath pan continuous heating that the pressure of take is 180 ℃ as 10 bar (Bar) temperature stirs 5 hours.After black powder being taken out after wait reactor is naturally cooling, then rinse with 500 ml deionized water, and overnight dry under 80 ℃ of baking ovens.The powder being dried (approximately 2.25 grams) is moved to containing passivity mist (5% H
2 aMP.AMp.Amp 95% Ar) under environment, with 600 ℃ of calcinings 4 hours, to produce nano level metal tin/carbon composite.
First, by 2.5 grams of graphite (Graphite), 2.5 grams of sodium nitrate (Sodium nitrate, NaNO
3) and 115 milliliters of sulfuric acid (Sulfuric acid, H
2sO
4), in the ice bath reaction bulb of 500 milliliters, evenly mix, and stir with magnetite.Then under agitation slowly add 7.5 grams of potassium permanganate (Potassium Permanganate, KMnO
4) and avoid reaction temperature to surpass 20 ℃.Then reaction bulb is moved to 35 ℃ of water-baths 30 minutes, after having reacted, in bottle, slowly add 115 ml deionized water, and make reaction temperature be warming up to 98 ℃ of reactions 15 minutes.Follow-up 350 ml deionized water and 23 milliliter of 35% hydrogen peroxide (Hydrogen peroxide, the H of reinjecting
2o
2), after waiting for that nature is cooling, reactant is washed till to neutrality with dialysis water-washing method, to prepare graphite oxide aqueous solution.Get the graphite oxide aqueous solution of 10 milliliters of 1wt%, and add 3.6 grams of glucose (>99.5%; Be preferably D (+) glucose), with 1.2g urea (>99.5%; ACROS), then with magnetite stir and allow glucose fully dissolve in 90 minutes.Follow-up 1 gram of micron order (50 μ m) manganese metal (>99% that adds; Sigma-Aldrich) stir half an hour.After being mixed evenly, mixed liquor is moved in the reactor of 100 milliliters, (if pressure is 5 bar, temperature is 150 ℃ as 180 ℃ as 10 bar (Bar) temperature to take pressure; If pressure is 24 bar, temperature is 220 ℃) oil bath pan continuous heating stir 5 hours.After waiting for that reactor is naturally cooling, black powder is taken out with 500 ml deionized water and rinsed, and overnight dry under 80 ℃ of baking ovens.The powder being dried is accredited as nanoscale carbonic acid manganese structure by XRD.By approximately 2.25 grams of powder that have been dried (as shown in Fig. 7 (a)), move to passivity gas (N again
2) environment under, with 400 ℃ calcining 4 to 10 hours, this composite material can, successfully by manganese carbonate, be transformed into the manganese oxide (as shown in Fig. 7 (b)) of tool electro-chemical activity after calcining.
Refer to Fig. 8, it is the XRD qualification result of above-mentioned composite material after calcining.Wherein (c) illustrates, before calcining, the manganese in composite material all exists with the form of manganese carbonate, and through 400 ℃ of calcinings, after 4 to 10 hours, the manganese in composite material is transformed into manganese oxide (as shown in (d) Fig. 8) from manganese carbonate.
The invention belongs to estimable innovation, dark tool industrial value, therefore file an application in accordance with the law.In addition, the present invention can make any modification by those of ordinary skills, but does not depart from scope as claimed in claims.
Claims (11)
1. carbon is an activated complex, and it comprises:
Several carbon allotropes;
The particle of several tool activity; And
The molecular a kind of three-dimensional of several carbohydrates is sticked together carbon material, and the particle coupling of itself and described tool activity so that the particle of described tool activity is coupled with described carbon allotrope, and and then makes described carbon allotrope storehouse each other.
2. carbon as claimed in claim 1 is activated complex, it is characterized in that, described carbon allotrope, be selected from by zero dimension carbon allotrope, one dimension carbon allotrope, Two-dimensional Carbon allotrope and the group that wherein two or more combinations forms arbitrarily, wherein this zero dimension carbon allotrope is selected from by nano carbon microsphere, carbon black, activated carbon powder and the group that wherein two or more combinations forms arbitrarily, this one dimension carbon allotrope is selected from by CNT (carbon nano-tube), graphitic carbon pipe, carbon fiber and the group that wherein two or more combinations forms arbitrarily, and this Two-dimensional Carbon allotrope is selected from Graphene, the group that native graphite and combination thereof form.
3. carbon as claimed in claim 1 is activated complex, it is characterized in that, the particle of described tool activity is selected from by silicon, tin, manganese, iron, cobalt, nickel, copper, germanium, antimony, bismuth, zinc, aluminium, cadmium metal and group that wherein two or more alloy, oxide, carbide, carbonate, phosphate and complex elements forms arbitrarily.
4. carbon as claimed in claim 3 is activated complex, it is characterized in that, the particle of described tool activity, to be embedded in the inside that this three-dimensional is sticked together carbon material, or be distributed on the surface of these several carbon allotropes, and the particle of described tool activity has the particle diameter of 1 ~ 100 nanometer, and in being the content of activated complex, this carbon accounts for 20% to 97% percentage by weight.
5. carbon as claimed in claim 1 is activated complex, it is characterized in that, those carbohydrate molecules are the structure with polynary ring, and be to be selected from by single candy, two candy, few candy, polysaccharide and group that wherein two or more combinations forms arbitrarily, this list candy is selected from by ribose, deoxyribose, glucose, fructose, galactolipin and group that wherein two or more combinations forms arbitrarily, and this pair of candy is selected from by sucrose, lactulose, lactose, maltose and group that wherein two or more combinations forms arbitrarily.
6. an activated complex, is characterized in that, this activated complex comprises:
Conductive materials;
The particle of tool activity; And
Carbon is matrix, and the particle coupling of itself and this tool activity so that the particle of this tool activity is coupled with this conductive materials, and makes minimized in size and the stabilisation of the particle of this tool activity.
7. activated complex as claimed in claim 6, it is characterized in that, this conductive materials is to be selected from by zero dimension carbon allotrope, one dimension carbon allotrope, Two-dimensional Carbon allotrope, and the group that forms of three-dimensional carbon allotrope, and this carbon is that the precursors of matrix is several carbohydrate molecules.
8. nano-scale carbon is a manufacture method for activated complex, it is characterized in that, the method comprises the following step:
(a) carbon allotrope, carbohydrate solution are mixed with the particle of micron order tool activity, to form mixed solution;
(b) under sealed environment, this mixed solution, under HTHP power, reaction is to form an intermediate product; And
(c) this intermediate product being calcined, is activated complex to produce this nano-scale carbon.
9. manufacture method as claimed in claim 8, it is characterized in that, this step (b) also comprises: (b1) this carbohydrate carbonization being become to a carbon is matrix, and by the particle of this micron order tool activity, is oxidized into one and is embedded in the nano level active compound particles that this carbon is matrix; And this step (c) also comprises: (c1) import a passivity gas, more than 400 ℃ by the reduction of this intermediate product, wherein this passivity gas is selected from by nitrogen, argon gas, carbon monoxide, hydrogen, diamine, lithium, sodium, potassium, magnesium vapor and group that wherein two or more combinations forms arbitrarily.
10. manufacture method as claimed in claim 8, is characterized in that, this step (b) is the temperature range at 100 ℃ ~ 350 ℃, and reacts under the pressure limit of 1 bar ~ 150 bar.
11. manufacture methods as claimed in claim 10, is characterized in that, this step (b) is the temperature range at 150 ℃ ~ 250 ℃, and reacts under the pressure limit of 4 bar ~ 25 bar.
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| CN107871877A (en) * | 2016-09-27 | 2018-04-03 | 三星电子株式会社 | O for cathode of air battery and lithium-air battery including it and the method for preparing positive pole |
| CN107665972A (en) * | 2017-07-05 | 2018-02-06 | 中国矿业大学 | A kind of Sn@C-material preparation methods of high-performance kalium ion battery negative material |
| CN107665972B (en) * | 2017-07-05 | 2020-04-17 | 中国矿业大学 | Preparation method of Sn @ C material of high-performance potassium ion battery negative electrode material |
| CN107482218A (en) * | 2017-07-18 | 2017-12-15 | 中国科学院化学研究所 | A kind of three-dimensional hollow material and preparation method thereof and the application in electrochemical energy storing device |
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