CN107134579A - A kind of preparation method of carbon material for positive conductive agent - Google Patents
A kind of preparation method of carbon material for positive conductive agent Download PDFInfo
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- CN107134579A CN107134579A CN201710250344.1A CN201710250344A CN107134579A CN 107134579 A CN107134579 A CN 107134579A CN 201710250344 A CN201710250344 A CN 201710250344A CN 107134579 A CN107134579 A CN 107134579A
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- carbon material
- catalyst
- preparation
- conductive agent
- positive conductive
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000006258 conductive agent Substances 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 40
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 26
- 230000015556 catabolic process Effects 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000001294 propane Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 11
- 238000005253 cladding Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000010306 acid treatment Methods 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000005034 decoration Methods 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 239000002699 waste material Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 description 18
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
Classifications
-
- 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
-
- 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 present invention relates to the preparation method of a kind of carbon material, especially a kind of carbon material for positive conductive agent, belong to lithium ion battery production technical field.It can realize prepared by the continuous reduction to catalyst feed during by present invention production catalyst, effectively improve production efficiency, while the catalyst quality of production is effectively ensured, also can effectively reduce energy consumption and reduce the waste of gaseous mixture；When further producing carbon material, production efficiency, reduction production cost can be effectively improved, energy consumption and waste is reduced；And the moving direction of the flow direction and material due to mixed gas is on the contrary, ensure that mixed gas can effectively ensure that product quality, reduce the waste of mixed gas and catalyst with material good contact and the reaction such as catalyst.
Description
Technical field
The present invention relates to the preparation method of a kind of carbon material, especially a kind of carbon material for positive conductive agent, belong to
Lithium ion battery production technical field.
Background technology
Conductive agent is one of important component of lithium ion cell electrode.It is conventional just as power-type lithium ion battery
Pole material, all very low but good high rate charge-discharge characteristic of the electrical conductivity of the positive electrode such as manganate, nitrate and longer
Service life it cannot be guaranteed that.This is the major issue faced during power lithium-ion battery is applied.Therefore, cyclical stability
The research and development of good novel conductive agent turn into an important topic of Study on Li-ion batteries.
In recent years, with the generally realization of a large amount of industrialized productions of nano-carbon material, nano-carbon material is applied to manganese
Acid lithium battery positive conductive agent.Perfect conductive mesh is formd using the pole piece of carbon material as lithium manganate cell positive electrode conductive agent
Network, is obviously reduced the internal resistance of cell, so that its heating is seldom and keeps good stability, big high rate performance, which has, substantially to be changed
It is kind so that battery capacity conservation rate is also apparently higher than the battery of other common positive conductive agent.
The content of the invention
The purpose of the present invention is that there is provided a kind of preparation of the carbon material for positive conductive agent in view of the shortcomings of the prior art
Method.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of carbon material for positive conductive agent, comprises the following steps：
The preparation of I, catalyst
1）It is 1 by weight by the CNT and water of acid treatment：70-90 is mixed, and obtains mixture；
2）Cladding：With peristaltic pump, into the mixture, the mixed solution and concentration of two-way instillation cobalt nitrate and manganese nitrate are
1mol/L ammonium bicarbonate soln, adjusts the pH of solution, untill solution colour is claret；Cobalt nitrate in the mixed solution
Concentration with manganese nitrate is respectively 1mol/L；
3）Filtering：The solution after cladding processing is filtered, obtained solid is washed to colourless, after 120-140 DEG C of condition is dried,
It is ground to the particle that particle diameter is 15 μm；
4）Aerobic breakdown：By the particle aerobic breakdown 30-50 minutes at 370-390 DEG C, black is changed into color；
5）Reduction：Particle after aerobic breakdown is handled 570-590 DEG C of reduction 60-120 of vacuum in the atmosphere of argon gas and hydrogen
Minute, produce catalyst；
Reduction is carried out in redox arrangement, and the device includes body of heater 10, the front portion of body of heater 10 be provided with body of heater
The air inlet 11 and discharge gate 13 of chamber connection, rear portion is provided with the gas outlet 12 connected with the inner chamber of body of heater 10 and charging aperture 14.Enter
Material mouth 14 is located at the top of body of heater 10, and discharge gate 13 is located at the bottom of body of heater 10, is easy to charging and discharge；Set on charging aperture 14
There is feed pipe 141, the top of feed pipe 141 is extended out and funnel from bottom to top, it is convenient to be added materials from charging aperture 14 to stove
In body 10.Drainage conduit 131 is provided with discharge gate 13, is easy to be connected with following process equipment or rewinding container or pipe material.Hydrogen
Gas and argon gas continue by a certain percentage from air inlet 11 be passed through the inner chamber of body of heater 10 in and fill the full inner chamber of body of heater 10 formed hydrogen and
Other gases produced in the gaseous mixture atmosphere of argon gas, unnecessary gas or reduction process can then be discharged from gas outlet 12, plus
Thermal can to the aerobic breakdown in body of heater 10 or body of heater 10 processing particle heat, aerobic breakdown handle particle from
After charging aperture 14 is entered in body of heater 10, discharge gate is pushed to by feed device, the particle of aerobic breakdown processing exists in the process
It is heated in gaseous mixture atmosphere and produces reduction reaction, thus, it is possible to realize prepared by the continuous reduction to catalyst feed, without frequency
It is numerous that body of heater 10 is cooled down, can effectively improve production efficiency, and the flow direction due to gaseous mixture with aerobic breakdown
The moving direction of the particle of reason is on the contrary, ensure that good contact and the reaction of the particle and gaseous mixture of aerobic breakdown processing, energy
The catalyst quality of production is enough effectively ensured, also can effectively reduce energy consumption and reduce the waste of gaseous mixture.
The feed device for the material in body of heater 10 to be pushed to discharge gate 13 from charging aperture 14 is provided with body of heater 10；Also
Including the heater for the material in heating furnace body 10 or body of heater 10（Not shown in figure）.Feed device includes being located at body of heater
Spiral Auger 20 and the drive device being arranged on body of heater 10 in 10, spiral Auger 20 are adapted with the inner chamber of body of heater 10, driven
Dynamic device is used to drive spiral Auger 20 to rotate；If spiral Auger 20 is hubbed in body of heater 10 by dry bearing 40, it can reduce
The frictional resistance that spiral Auger 20 is subject to when rotating, improves the power output conversion ratio of drive device, reduces energy consumption, can also keep away
Exempt from spiral Auger 20 to wear and tear with body of heater 10, increase the service life, reduce fault rate；Drive device employs conventional driving
Motor 31, the output shaft of motor 31 is connected by yielding coupling 32 with spiral Auger 20, convenient for assembly, it helps to subtract
The influence that small manufacturing and positioning errors are rotated to spiral Auger 20, reduces the vibration and swing of body of heater 10 and spiral Auger 20, has
Help reduction rate of breakdown, increase the service life.
The preparation of II, carbon materials
1）Catalyst is placed in the gaseous mixture of argon gas and propane under vacuum, propane is adsorbed in catalyst surface；
2）3-5h is stopped under the conditions of 680-720 DEG C, propane is decomposed into carbon and hydrogen；
3）Hydrogen is desorbed from catalyst surface, carbon material is produced；
The preparation of carbon material is carried out in continuous growing device, and the device includes：Body of heater is grown, growth body of heater is included sequentially
The charging with the intracavity inter-connection of growth body of heater is provided with connected preceding pedestal 21, roller 22 and rear pedestal 23, preceding pedestal 21
The discharge gate 242 and air inlet with the intracavity inter-connection of growth body of heater are provided with mouth 241 and exhaust outlet 252, rear pedestal 23
251, roller 22 is driven by a drive device and can rotated relative to preceding pedestal 21 and rear pedestal 23, and the relatively preceding pedestal 21 of roller 22
When being rotated with rear pedestal 23 material in growth furnace body can be driven to move from front to back；Heater, for growth body of heater or
Material in growth furnace body is heated（Not shown in figure）.Growth body of heater and heater are arranged at the hot box 30
It is interior.The mixed gas of certain proportion argon gas and propane is passed into growth furnace body from air inlet 251 and completely grows body of heater to fill
Inner chamber, unnecessary and reacted gas then discharged from exhaust outlet 252, and catalyst is entered in growth furnace body from charging aperture 241,
Reacted during being moved rearwards by with propane and grow carbon material, finally discharged again from discharge gate 242, thus achieve carbon
Material can be maintained at the temperature of needs by the continuous production of material, in the process, heater, while roller 22 can be right
Catalyst raw material, carbon material in growth furnace body can be overturn so that catalyst can fully, uniformly with propane contact and
Reaction, thus, it is possible to realize prepared by the continuous growth to carbon material, without frequently heating and cooling growth body of heater, changes gaseous mixture
Body and replacing material, can effectively improve production efficiency, reduction production cost, reduce energy consumption and waste；And due to mixing
The flow direction of gas and the moving direction of material are on the contrary, ensure that mixed gas can be with the material good contact such as catalyst
With reaction, product quality is can effectively ensure that, the waste of mixed gas and catalyst is reduced.
Roller 22 is downwardly inclined with the horizontal an angle from front to back, and can drive growth body of heater when rotating roller 22
Interior material is moved from front to back, can also keep the smooth of the inwall of roller 22, prevents from causing the carbon material grown out punching
Hit, it is ensured that product quality, the angle a's between roller 22 and horizontal plane is preferably sized to 12-17 degree, the angle bottom roll 22
The translational speed of interior material can preferably meet fully reaction and ensure the requirement of production efficiency.
External gear 26 is provided with the outer wall of roller 22, drive device includes motor 31 and is arranged on motor 31
Driving gear 32 on output shaft, driving gear 32 is meshed with external gear 26, and the motor 31 made can drive roller 22
Rotate, and the front and rear of roller 22 is provided with external gear 26 in the present embodiment, while driven by same motor 31,
The uniform force of roller 22 is ensure that, the unbalance stress of roller 22 is prevented and damages.
Preferably, the pH to 7-10 of solution is adjusted in encapsulation steps, reaction temperature is normal temperature.
Preferably, the vacuum pressure≤0.02MPa reduced described in I, argon gas：Hydrogen=4:1.
Preferably, pressure≤0.02MPa of vacuum described in II, argon gas：Propane=1:5.
Preferably, the carbon material is CNT.
Carbon material prepared by the above method impregnates 0.8-1.2h in concentrated nitric acid, and carrying out strong acid surface to carbon material repaiies
Decorations, then by 3 μm of ball mill grinding of the carbon material of strong acid surface modification, then are made positive conductive agent.
The CNT of acid treatment, i.e., with the sour reflux oxidation nano-sized carbon of mixture Strong oxdiative of nitric acid, sulfuric acid and pure water
Pipe.It is first by CNT in the pre-dispersed 1h of mixture of nitric acid, sulfuric acid and pure water, then react 2h at 90 DEG C, then with pure
In 110 DEG C of dry 24h after water and alcohol washes, the CNT of acid treatment is produced.
In the preparation process of carbon material, propane decomposes in catalyst surface and obtains carbon and hydrogen, and then hydrogen is from catalysis
Agent surface desorption, carbon dissolution is in catalyst matrix and forming cobalt carbide, and cobalt carbide is not so good as cobalt and graphite stable, therefore formed
Cobalt carbide is decomposed into cobalt and graphite quickly.Because the formation of graphite linings will produce pressure difference, therefore catalyst cobalt will be extruded.Work as cobalt
It is exposed to after being extruded under propane environment, therefore can continues to adsorb propane, carbon materials is formed after the process reaches balance
Material.
Beneficial effects of the present invention：The continuous reduction to catalyst feed can be realized during by present invention production catalyst
Prepare, effectively improve production efficiency, while the catalyst quality of production is effectively ensured, also can effectively reduce energy consumption and reduce mixed
Close the waste of gas；When further producing carbon material, production efficiency, reduction production cost can be effectively improved, energy consumption and wave is reduced
Take；And the moving direction of the flow direction and material due to mixed gas is on the contrary, ensure that mixed gas can be with catalysis
The material such as agent good contact and reaction, can effectively ensure that product quality, reduce the waste of mixed gas and catalyst.
Brief description of the drawings
Fig. 1 is the structural representation of redox arrangement；
Fig. 2 is the structural representation of continuous growing device.
Embodiment
In order that those skilled in the art more fully understand technical scheme, with reference to specific embodiment to this
Invention is described in further detail.
Embodiment 1：The preparation of catalyst
1）The CNT of 5g acid treatments and 400g water are mixed to get mixture；
2）Cladding：Under normal temperature condition, with peristaltic pump into mixture two-way instillation concentration be respectively 1mol/L cobalt nitrate and
The mixed solution of manganese nitrate and 1mol/L ammonium bicarbonate soln, the pH of regulation solution is 7, and claret is changed into solution colour
Untill；
3）Filtering：The solution after cladding processing is filtered, obtained solid is washed to colourless, after 130 DEG C are dried, grain is ground to
The particle that 15 μm of footpath；
4）Aerobic breakdown：By the particle after milled processed at 380 DEG C aerobic breakdown 40 minutes, be changed into black to color；
5）Reduction：Argon gas and hydrogen press 4:1 constant is from the air inlet 11 of redox arrangement is passed through the inner chamber of body of heater 10
Form the mixed atmosphere of hydrogen and argon gas, control vacuum pressure for 0.02MPa, produced in unnecessary gas or reduction process its
He can then discharge at gas from gas outlet 12, and the particle of aerobic breakdown processing is after charging aperture 14 is entered in body of heater 10, heating
The particle that aerobic breakdown is handled is heated to 580 DEG C of simultaneously continued reduction 90 minutes by device, and discharge gate 13 is pushed to by feed device, real
Now prepared by the continuous reduction to catalyst feed.
Embodiment 2：The preparation of catalyst
1）The CNT of 5g acid treatments and 450g water are mixed to get mixture；
2）Cladding：With peristaltic pump, into mixture, two-way instillation concentration is respectively the mixed solution of 1mol/L cobalt nitrates and manganese nitrate
And the ammonium bicarbonate soln that concentration is 1mol/L, the pH of regulation solution is 8.5, untill solution colour is claret；
3）The solution after cladding processing is filtered, obtained solid is washed to colourless, after 140 DEG C of conditions are dried, grain is ground to
Footpath is 15 μm of particle；
4）Aerobic breakdown：By particle at 390 DEG C aerobic breakdown 30 minutes, be changed into black to color；
5）Reduction：Argon gas and hydrogen press 4:1 constant is from the air inlet 11 of redox arrangement is passed through the inner chamber of body of heater 10
Form the mixed atmosphere of hydrogen and argon gas, control vacuum pressure for 0.02MPa, produced in unnecessary gas or reduction process its
He can then discharge at gas from gas outlet 12, and the particle of aerobic breakdown processing is after charging aperture 14 is entered in body of heater 10, heating
The particle that aerobic breakdown is handled is heated to 590 DEG C of simultaneously continued reduction 60 minutes by device, and discharge gate 13 is pushed to by feed device, real
Now prepared by the continuous reduction to catalyst feed.
Embodiment 3：The preparation of catalyst
1）The CNT of 5g acid treatments and 350g water are mixed to get mixture；
2）Cladding：With peristaltic pump, into mixture, two-way instillation concentration is respectively the mixed solution of 1mol/L cobalt nitrates and manganese nitrate
And the ammonium bicarbonate soln that concentration is 1mol/L, the pH of regulation solution is 10, untill solution colour is claret；
3）The solution after cladding processing is filtered, obtained solid is washed to colourless, after 120 DEG C of conditions are dried, grain is ground to
Footpath is 15 μm of particle；
4）Aerobic breakdown：By particle at 370 DEG C aerobic breakdown 50 minutes, be changed into black to color；
5）Reduction：Argon gas and hydrogen press 4:1 constant is from the air inlet 11 of redox arrangement is passed through the inner chamber of body of heater 10
Form the mixed atmosphere of hydrogen and argon gas, control vacuum pressure for 0.02MPa, produced in unnecessary gas or reduction process its
He can then discharge at gas from gas outlet 12, and the particle of aerobic breakdown processing is after charging aperture 14 is entered in body of heater 10, heating
The particle that aerobic breakdown is handled is heated to 570 DEG C of simultaneously continued reduction 120 minutes by device, and discharge gate 13 is pushed to by feed device,
Realize prepared by the continuous reduction to catalyst feed.
Embodiment 4：The preparation of CNT
Argon gas and propane are pressed 1:The gaseous mixture of 5 ratios mixing is passed into growth furnace body from air inlet 251, controls vacuum pressure
For 0.02MPa, catalyst prepared by embodiment 1 is entered in growth furnace body from charging aperture 241, is heated to 700 DEG C and is kept
4h, catalyst reacts during being moved rearwards by with propane so that propane is decomposed into carbon and hydrogen, and hydrogen is from catalyst surface
Desorption is discharged from exhaust outlet 252, so as to grow carbon material, carbon material is finally discharged from discharge gate 242 again, realizes carbon material
Continuous production.
Embodiment 5：
Carbon material prepared by embodiment 4 impregnates 1h in concentrated nitric acid, strong acid surface modification is carried out to carbon material, then by strong acid
Then the carbon material ball mill grinding of surface modification is made positive conductive agent to 3 μm of particle diameter.
Claims (6)
1. the preparation method of a kind of carbon material for positive conductive agent, it is characterised in that comprise the following steps：
The preparation of I, catalyst
1）It is 1 by weight by the CNT and water of acid treatment：70-90 is mixed, and obtains mixture；
2）Cladding：With peristaltic pump, into the mixture, the mixed solution and concentration of two-way instillation cobalt nitrate and manganese nitrate are
1mol/L ammonium bicarbonate soln, adjusts the pH of solution, untill solution colour is claret；Cobalt nitrate in the mixed solution
Concentration with manganese nitrate is respectively 1mol/L；
3）Filtering：The solution after cladding processing is filtered, obtained solid is washed to colourless, after 120-140 DEG C of condition is dried,
It is ground to the particle that particle diameter is 15 μm；
4）Aerobic breakdown：By the particle aerobic breakdown 30-50 minutes at 370-390 DEG C, black is changed into color；
5）Reduction：Particle after aerobic breakdown is handled 570-590 DEG C of reduction 60-120 of vacuum in the atmosphere of argon gas and hydrogen
Minute, produce catalyst；
The preparation of II, carbon materials
1）Catalyst is placed in the gaseous mixture of argon gas and propane under vacuum, propane is adsorbed in catalyst surface；
2）3-5h is stopped under the conditions of 680-720 DEG C, propane is decomposed into carbon and hydrogen；
3）Hydrogen is desorbed from catalyst surface, carbon material is produced.
2. the preparation method of the carbon material according to claim 1 for positive conductive agent, it is characterised in that encapsulation steps
The pH to 7-10 of middle regulation solution, reaction temperature is normal temperature.
3. the preparation method of the carbon material according to claim 1 for positive conductive agent, it is characterised in that described in I
Vacuum pressure≤0.02MPa of reduction, argon gas：Hydrogen=4:1.
4. the preparation method of the carbon material according to claim 1 for positive conductive agent, it is characterised in that described in II
Pressure≤0.02MPa of vacuum, argon gas：Propane=1:5.
5. the preparation method of the carbon material according to claim 1 for positive conductive agent, it is characterised in that the carbon materials
Material is CNT.
6. the preparation method of the carbon material for positive conductive agent according to claim any one of 1-5, its feature exists
In, carbon material is impregnated into 0.8-1.2h in concentrated nitric acid, to carbon material carry out strong acid surface modification, then strong acid surface is repaiied
The carbon material ball mill grinding of decorations is to 3 μm, then positive conductive agent is made.
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| CN201710250344.1A CN107134579B (en) | 2017-04-17 | 2017-04-17 | Preparation method of carbon material for positive electrode conductive agent |
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| CN201710250344.1A CN107134579B (en) | 2017-04-17 | 2017-04-17 | Preparation method of carbon material for positive electrode conductive agent |
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| CN107134579B CN107134579B (en) | 2020-03-17 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108325492A (en) * | 2018-03-14 | 2018-07-27 | 荆门市熊兴化工有限公司 | A kind of nitration processes and device preparing H acid |
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| CN103170334A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Carbon-supported cobalt oxide catalyst and preparation and application thereof |
| CN103447039A (en) * | 2012-05-30 | 2013-12-18 | 南京大学 | Cobalt-base catalyst taking carbon nano tubes as carriers and applications thereof |
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| CN103170334A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Carbon-supported cobalt oxide catalyst and preparation and application thereof |
| CN103447039A (en) * | 2012-05-30 | 2013-12-18 | 南京大学 | Cobalt-base catalyst taking carbon nano tubes as carriers and applications thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108325492A (en) * | 2018-03-14 | 2018-07-27 | 荆门市熊兴化工有限公司 | A kind of nitration processes and device preparing H acid |
| CN108325492B (en) * | 2018-03-14 | 2023-12-19 | 湖北丽康源化工有限公司 | Nitration technology and device for preparing H acid |
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