CN107134579B - Preparation method of carbon material for positive electrode conductive agent - Google Patents
Preparation method of carbon material for positive electrode conductive agent Download PDFInfo
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- CN107134579B CN107134579B CN201710250344.1A CN201710250344A CN107134579B CN 107134579 B CN107134579 B CN 107134579B CN 201710250344 A CN201710250344 A CN 201710250344A CN 107134579 B CN107134579 B CN 107134579B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000006258 conductive agent Substances 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 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
- 239000007789 gas Substances 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 23
- 238000000354 decomposition reaction Methods 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001294 propane Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 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
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- 238000000227 grinding Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000033116 oxidation-reduction process Effects 0.000 claims description 6
- 238000005406 washing Methods 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
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 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
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 230000002457 bidirectional effect Effects 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 238000006722 reduction reaction Methods 0.000 description 11
- 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
- 238000007599 discharging Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 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
- 239000008213 purified water Substances 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 238000005299 abrasion Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
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- 208000021302 gastroesophageal reflux disease Diseases 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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Images
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 invention relates to a carbon material, in particular to a preparation method of the carbon material for a positive electrode conductive agent, belonging to the technical field of lithium ion battery production. When the catalyst is produced, the catalyst material can be continuously reduced and prepared, so that the production efficiency is effectively improved, the quality of the produced catalyst is effectively ensured, and the energy consumption and the waste of mixed gas can be effectively reduced; when the carbon material is further produced, the production efficiency can be effectively improved, the production cost can be reduced, and the energy consumption and waste can be reduced; and because the flow direction of the mixed gas is opposite to the moving direction of the materials, the mixed gas can be ensured to be in good contact and reaction with the materials such as the catalyst, the product quality can be effectively ensured, and the waste of the mixed gas and the catalyst is reduced.
Description
Technical Field
The invention relates to a carbon material, in particular to a preparation method of the carbon material for a positive electrode conductive agent, belonging to the technical field of lithium ion battery production.
Background
Conductive agents are one of the important components of lithium ion battery electrodes. As a common positive electrode material for a power lithium ion battery, the conductivity of positive electrode materials such as manganate and nitrate is very low, but good high-rate charge-discharge characteristics and long service life cannot be guaranteed. This is an important issue facing power lithium ion battery applications. Therefore, research and development of a novel conductive agent with good cycle stability has become an important issue in the research of lithium ion batteries.
In recent years, with the widespread realization of the mass industrial production of the nano carbon material, the nano carbon material has been applied to a positive electrode conductive agent of a lithium manganate battery. The carbon material is used as the pole piece of the lithium manganate battery positive electrode conductive agent to form a perfect conductive network, so that the internal resistance of the battery is obviously reduced, the battery generates little heat and keeps good stability, the high rate performance is obviously improved, and the capacity retention rate of the battery is also obviously higher than that of other batteries with common positive electrode conductive agents.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon material for a positive electrode conductive agent, aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a carbon material for a positive electrode conductive agent, comprising the steps of:
preparation of the catalyst
1) Mixing the carbon nano-tube treated by acid with water according to the weight ratio of 1: 70-90 to obtain a mixture;
2) coating: a peristaltic pump is used for dropping a mixed solution of cobalt nitrate and manganese nitrate and an ammonium bicarbonate solution with the concentration of 1mol/L into the mixture in a bidirectional way, and the pH value of the solution is adjusted until the color of the solution is wine red; the concentrations of cobalt nitrate and manganese nitrate in the mixed solution are respectively 1 mol/L;
3) and (3) filtering: filtering the solution after coating treatment, washing the obtained solid to be colorless, drying at the temperature of 120-140 ℃, and grinding to particles with the particle size of 15 mu m;
4) aerobic decomposition: carrying out aerobic decomposition on the particles at the temperature of 370-390 ℃ for 30-50 minutes until the color is changed into black;
5) reduction: reducing the particles subjected to the aerobic decomposition treatment in an argon and hydrogen atmosphere at the temperature of 570-590 ℃ for 60-120 minutes to obtain a catalyst;
the reduction is carried out in an oxidation-reduction device, which comprises a furnace body 10, wherein the front part of the furnace body 10 is provided with an air inlet 11 and a discharge outlet 13 which are communicated with the inner cavity of the furnace body, and the rear part is provided with an air outlet 12 and a feed inlet 14 which are communicated with the inner cavity of the furnace body 10. The feeding hole 14 is positioned at the top end of the furnace body 10, and the discharging hole 13 is positioned at the bottom end of the furnace body 10, so that feeding and discharging are facilitated; the feed inlet 14 is provided with a feed pipe 141, and the upper part of the feed pipe 141 is expanded from bottom to top to form a funnel shape, so that materials can be conveniently added into the furnace body 10 from the feed inlet 14. The discharge opening 13 is provided with a discharge pipe 131 which is convenient to be connected with subsequent processing equipment or a material receiving container or a material pipeline. Hydrogen and argon are continuously introduced into the inner cavity of the furnace body 10 from the gas inlet 11 according to a certain proportion to fill the inner cavity of the furnace body 10 to form a mixed gas atmosphere of hydrogen and argon, redundant gas or other gas generated in the reduction process can be discharged from the gas outlet 12, the heating device can heat the furnace body 10 or particles subjected to aerobic decomposition treatment in the furnace body 10, the particles subjected to the aerobic decomposition treatment enter the furnace body 10 from the feed inlet 14 and are pushed to the discharge outlet by the feeding device, and the particles subjected to the aerobic decomposition treatment are heated in the mixed gas atmosphere to generate reduction reaction in the process, so that the continuous reduction preparation of the catalyst material can be realized, the furnace body 10 is not required to be frequently cooled, the production efficiency can be effectively improved, and good contact and reaction between the particles subjected to the aerobic decomposition treatment and the mixed gas can be ensured because the flow direction of the mixed gas is opposite to the movement direction of the particles subjected to the aerobic decomposition treatment, the quality of the produced catalyst can be effectively ensured, and the energy consumption and the waste of the mixed gas can be effectively reduced.
The furnace body 10 is provided with a feeding device which is used for pushing the materials in the furnace body 10 from the feeding hole 14 to the discharging hole 13; and a heating device (not shown) for heating the furnace body 10 or the materials in the furnace body 10. The feeding device comprises a spiral auger 20 arranged in the furnace body 10 and a driving device arranged on the furnace body 10, the spiral auger 20 is matched with the inner cavity of the furnace body 10, and the driving device is used for driving the spiral auger 20 to rotate; the spiral auger 20 is pivoted in the furnace body 10 through a plurality of bearings 40, so that the frictional resistance borne by the spiral auger 20 during rotation can be reduced, the output power conversion rate of the driving device is improved, the energy consumption is reduced, the abrasion between the spiral auger 20 and the furnace body 10 can be avoided, the service life is prolonged, and the failure rate is reduced; the driving device adopts the driving motor 31 which is commonly used, the output shaft of the driving motor 31 is connected with the spiral auger 20 through the elastic coupling 32, the assembly is convenient, the influence of the processing and assembling errors on the rotation of the spiral auger 20 is reduced, the vibration and the swing of the furnace body 10 and the spiral auger 20 are reduced, the fault occurrence rate is reduced, and the service life is prolonged.
Preparation of carbon Material
1) Putting the catalyst in a mixed gas of argon and propane under vacuum to make the propane adsorbed on the surface of the catalyst;
2) standing at the temperature of 680-720 ℃ for 3-5h to decompose the propane into carbon and hydrogen;
3) desorbing hydrogen from the surface of the catalyst to obtain a carbon material;
the preparation of the carbon material is carried out in a continuous growth apparatus comprising: the growth furnace body comprises a front base 21, a roller 22 and a rear base 23 which are sequentially connected, a feed inlet 241 and an exhaust outlet 252 which are communicated with the inner cavity of the growth furnace body are arranged on the front base 21, a discharge outlet 242 and an air inlet 251 which are communicated with the inner cavity of the growth furnace body are arranged on the rear base 23, the roller 22 is driven by a driving device to rotate relative to the front base 21 and the rear base 23, and when the roller 22 rotates relative to the front base 21 and the rear base 23, the material in the growth furnace body can be driven to move from front to back; and the heating device is used for heating the growth furnace body or materials in the growth furnace body (not shown in the figure). The growth furnace body and the heating device are both arranged in the heat insulation box 30. A mixed gas of argon and propane with a certain proportion is introduced into the growth furnace body from the gas inlet 251 to fill the inner cavity of the growth furnace body, redundant and reacted gas is discharged from the gas outlet 252, the catalyst enters the growth furnace body from the feed inlet 241, reacts with propane in the backward moving process to grow a carbon material, and is finally discharged from the discharge outlet 242, so that the continuous production of the carbon material is realized, in the process, the heating device can keep the material at a required temperature, meanwhile, the roller 22 can turn over the catalyst raw material and the carbon material in the growth furnace body, so that the catalyst can fully and uniformly contact and react with propane, the continuous growth preparation of the carbon material can be realized, the growth furnace body does not need to be frequently heated and cooled, the mixed gas is replaced, the material is not needed to be replaced, the production efficiency can be effectively improved, and the production cost is reduced, energy consumption and waste are reduced; and because the flow direction of the mixed gas is opposite to the moving direction of the materials, the mixed gas can be ensured to be in good contact and reaction with the materials such as the catalyst, the product quality can be effectively ensured, and the waste of the mixed gas and the catalyst is reduced.
The roller 22 inclines downwards from front to back at an included angle with the horizontal plane, so that the roller 22 can drive materials in the growth furnace body to move from front to back when rotating, the smoothness of the inner wall of the roller 22 can be kept, the impact on the grown carbon material is prevented, the product quality is ensured, the size of the included angle a between the roller 22 and the horizontal plane is preferably 12-17 degrees, and the moving speed of the materials in the roller 22 at the angle can better meet the requirements of full reaction and production efficiency.
The outer wall of the drum 22 is provided with the external gear 26, the driving device comprises a driving motor 31 and a driving gear 32 arranged on an output shaft of the driving motor 31, the driving gear 32 is engaged with the external gear 26, so that the driving motor 31 can drive the drum 22 to rotate, in addition, the external gear 26 is arranged at the front part and the rear part of the drum 22 in the embodiment, and simultaneously, the driving is carried out by the same driving motor 31, the uniform stress of the drum 22 can be ensured, and the damage of the drum 22 due to the nonuniform stress can be prevented.
Preferably, the pH of the solution is adjusted to 7-10 in the coating step, and the reaction temperature is normal temperature.
Preferably, the vacuum pressure of the reduction in I is less than or equal to 0.02MPa, and the ratio of argon: hydrogen =4: 1.
Preferably, the pressure of the vacuum in II is less than or equal to 0.02MPa, and the ratio of argon: propane =1: 5.
Preferably, the carbon material is carbon nanotubes.
Soaking the carbon material prepared by the method in concentrated nitric acid for 0.8-1.2h, performing strong acid surface modification on the carbon material, grinding the carbon material subjected to strong acid surface modification by using a ball mill for 3 mu m, and preparing the positive electrode conductive agent.
The carbon nanotubes treated by acid are prepared by using a mixture of nitric acid, sulfuric acid and purified water to oxidize the carbon nanotubes by strong acid reflux. Firstly, pre-dispersing carbon nanotubes in a mixture of nitric acid, sulfuric acid and purified water for 1h, then reacting for 2h at 90 ℃, then washing with purified water and alcohol, and drying at 110 ℃ for 24h to obtain the acid-treated carbon nanotubes.
In the preparation process of the carbon material, propane is decomposed on the surface of the catalyst to obtain carbon and hydrogen, then the hydrogen is desorbed from the surface of the catalyst, the carbon is dissolved in the catalyst matrix and forms cobalt carbide, and the cobalt carbide is not as stable as cobalt and graphite, so the formed cobalt carbide is quickly decomposed into cobalt and graphite. The catalyst cobalt will be extruded as the formation of the graphite layer will create a pressure differential. When the cobalt is extruded, it is exposed to a propane environment, so that it can continue to adsorb propane, and when the process reaches equilibrium, a carbon material is formed.
The invention has the beneficial effects that: when the catalyst is produced, the catalyst material can be continuously reduced and prepared, so that the production efficiency is effectively improved, the quality of the produced catalyst is effectively ensured, and the energy consumption and the waste of mixed gas can be effectively reduced; when the carbon material is further produced, the production efficiency can be effectively improved, the production cost can be reduced, and the energy consumption and waste can be reduced; and because the flow direction of the mixed gas is opposite to the moving direction of the materials, the mixed gas can be ensured to be in good contact and reaction with the materials such as the catalyst, the product quality can be effectively ensured, and the waste of the mixed gas and the catalyst is reduced.
Drawings
FIG. 1 is a schematic diagram of a redox device;
FIG. 2 is a schematic view of the structure of the continuous growth apparatus.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention is further described in detail with reference to the specific embodiments below.
Example 1: preparation of the catalyst
1) Mixing 5g of the acid-treated carbon nanotubes with 400g of water to obtain a mixture;
2) coating: under the condition of normal temperature, a peristaltic pump is used for dropping a mixed solution of cobalt nitrate and manganese nitrate with the concentration of 1mol/L and a 1mol/L ammonium bicarbonate solution into the mixture in two directions, the pH value of the solution is adjusted to 7 until the color of the solution becomes wine red;
3) and (3) filtering: filtering the coated solution, washing the obtained solid to be colorless, drying at 130 ℃, and grinding to particles with the particle size of 15 mu m;
4) aerobic decomposition: decomposing the milled particles at 380 ℃ for 40 minutes in the presence of oxygen until the color becomes black;
5) reduction: argon and hydrogen are continuously introduced into the inner cavity of the furnace body 10 from the air inlet 11 of the oxidation-reduction device according to the ratio of 4:1 to form a mixed atmosphere of hydrogen and argon, the vacuum pressure is controlled to be 0.02MPa, redundant gas or other gases generated in the reduction process can be discharged from the air outlet 12, after the particles subjected to the aerobic decomposition treatment enter the furnace body 10 from the feed inlet 14, the particles subjected to the aerobic decomposition treatment are heated to 580 ℃ by the heating device and are continuously reduced for 90 minutes, and the particles are pushed to the discharge outlet 13 by the feeding device, so that the continuous reduction preparation of the catalyst material is realized.
Example 2: preparation of the catalyst
1) Mixing 5g of the acid-treated carbon nanotubes with 450g of water to obtain a mixture;
2) coating: a peristaltic pump is used for dropping a mixed solution of cobalt nitrate and manganese nitrate with the concentration of 1mol/L and an ammonium bicarbonate solution with the concentration of 1mol/L into the mixture in a two-way manner, the pH value of the solution is adjusted to 8.5 until the color of the solution is wine red;
3) filtering the coated solution, washing the obtained solid to be colorless, drying at 140 ℃, and grinding to obtain particles with the particle size of 15 mu m;
4) aerobic decomposition: aerobically decomposing the granules at 390 ℃ for 30 minutes until the color becomes black;
5) reduction: argon and hydrogen are continuously introduced into the inner cavity of the furnace body 10 from the air inlet 11 of the oxidation-reduction device according to the ratio of 4:1 to form a mixed atmosphere of hydrogen and argon, the vacuum pressure is controlled to be 0.02MPa, redundant gas or other gases generated in the reduction process can be discharged from the air outlet 12, after the particles subjected to the aerobic decomposition treatment enter the furnace body 10 from the feed inlet 14, the particles subjected to the aerobic decomposition treatment are heated to 590 ℃ by the heating device and are continuously reduced for 60 minutes, and the particles are pushed to the discharge outlet 13 by the feeding device, so that the continuous reduction preparation of the catalyst material is realized.
Example 3: preparation of the catalyst
1) Mixing 5g of the acid-treated carbon nanotubes with 350g of water to obtain a mixture;
2) coating: a peristaltic pump is used for dropping a mixed solution of cobalt nitrate and manganese nitrate with the concentration of 1mol/L and an ammonium bicarbonate solution with the concentration of 1mol/L into the mixture in a two-way manner, the pH value of the solution is adjusted to 10 until the color of the solution is wine red;
3) filtering the coated solution, washing the obtained solid to be colorless, drying at 120 ℃, and grinding to obtain particles with the particle size of 15 mu m;
4) aerobic decomposition: aerobically decomposing the granules at 370 ℃ for 50 minutes until the color becomes black;
5) reduction: argon and hydrogen are continuously introduced into the inner cavity of the furnace body 10 from the air inlet 11 of the oxidation-reduction device according to the ratio of 4:1 to form a mixed atmosphere of hydrogen and argon, the vacuum pressure is controlled to be 0.02MPa, redundant gas or other gases generated in the reduction process can be discharged from the air outlet 12, after the particles subjected to the aerobic decomposition treatment enter the furnace body 10 from the feed inlet 14, the particles subjected to the aerobic decomposition treatment are heated to 570 ℃ by the heating device and are continuously reduced for 120 minutes, and the particles are pushed to the discharge outlet 13 by the feeding device, so that the continuous reduction preparation of the catalyst material is realized.
Example 4: preparation of carbon nanotubes
Introducing mixed gas of argon and propane mixed according to the ratio of 1:5 into a growth furnace body from an air inlet 251, controlling the vacuum pressure to be 0.02MPa, introducing the catalyst prepared in example 1 into the growth furnace body from an inlet 241, heating to 700 ℃ and keeping for 4h, reacting the catalyst with propane in the backward moving process to decompose propane into carbon and hydrogen, desorbing the hydrogen from the surface of the catalyst and discharging from an exhaust port 252 so as to grow a carbon material, and finally discharging the carbon material from a discharge port 242 so as to realize continuous production of the carbon material.
Example 5:
the carbon material prepared in example 4 was immersed in concentrated nitric acid for 1 hour, and subjected to strong acid surface modification, and then the carbon material subjected to strong acid surface modification was ground to a particle size of 3 μm by a ball mill, and then a positive electrode conductive agent was prepared.
Claims (3)
1. A method for preparing a carbon material for a positive electrode conductive agent, characterized by comprising the steps of:
preparation of the catalyst
1) Mixing the carbon nano-tube treated by acid with water according to the weight ratio of 1: 70-90 to obtain a mixture;
2) coating: a peristaltic pump is used for dropping a mixed solution of cobalt nitrate and manganese nitrate and an ammonium bicarbonate solution with the concentration of 1mol/L into the mixture in a bidirectional way, and the pH value of the solution is adjusted until the color of the solution is wine red; the concentrations of cobalt nitrate and manganese nitrate in the mixed solution are respectively 1 mol/L;
3) and (3) filtering: filtering the solution after coating treatment, washing the obtained solid to be colorless, drying at the temperature of 120-140 ℃, and grinding to particles with the particle size of 15 mu m;
4) aerobic decomposition: carrying out aerobic decomposition on the particles at the temperature of 370-390 ℃ for 30-50 minutes until the color is changed into black;
5) reduction: reducing the particles subjected to the aerobic decomposition treatment in an argon and hydrogen atmosphere at the temperature of 570-590 ℃ for 60-120 minutes to obtain a catalyst;
the reduction is carried out in an oxidation-reduction device, the oxidation-reduction device comprises a furnace body (10), the front part of the furnace body (10) is provided with an air inlet (11) and a discharge outlet (13) which are communicated with an inner cavity of the furnace body (10), the rear part of the furnace body is provided with an air outlet (12) and a feed inlet (14) which are communicated with the inner cavity of the furnace body (10), the feed inlet (14) is positioned at the top end of the furnace body (10), and the discharge outlet (13) is positioned at the bottom end of the furnace body (10; the furnace body (10) is provided with a feeding device which is used for pushing the materials in the furnace body (10) to the discharge hole (13) from the feed hole (14); the furnace body (10) and the heating device are both positioned in the heat insulation box;
the vacuum pressure of the reduction in I is less than or equal to 0.02MPa, and the argon gas: hydrogen 4: 1;
preparation of carbon Material
1) Putting the catalyst in a mixed gas of argon and propane under vacuum to make the propane adsorbed on the surface of the catalyst;
2) standing at the temperature of 680-720 ℃ for 3-5h to decompose the propane into carbon and hydrogen;
3) desorbing hydrogen from the surface of the catalyst to obtain a carbon material;
the preparation of the carbon material is carried out in a growth furnace body, the growth furnace body comprises a front base (21), a roller (22) and a rear base (23) which are connected in sequence, a feed inlet (241) and an exhaust outlet (252) which are communicated with the inner cavity of the growth furnace body are arranged on the front base (21), a discharge outlet (242) and an air inlet (251) which are communicated with the inner cavity of the growth furnace body are arranged on the rear base (23), the roller (22) is driven by a driving device to rotate relative to the front base (21) and the rear base (23), and when the roller (22) rotates relative to the front base (21) and the rear base (23), the material in the growth furnace body can be driven to move from front to back;
in II, the vacuum pressure is less than or equal to 0.02MPa, and the argon gas: propane 1: 5.
2. The method for producing a carbon material for a positive electrode conductive agent according to claim 1, wherein the pH of the solution is adjusted to 7 to 10 in the coating step, and the reaction temperature is room temperature.
3. The method for producing a carbon material for a positive electrode conductive agent according to any one of claims 1 to 2, wherein the carbon material is immersed in concentrated nitric acid for 0.8 to 1.2 hours, the carbon material is subjected to strong acid surface modification, and then the carbon material subjected to strong acid surface modification is ground to 3 μm with a ball mill and then manufactured into the positive electrode conductive agent.
Priority Applications (1)
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