CN108190889A - A kind of method for preparing low impurity high power capacity ultracapacitor activated carbon - Google Patents

A kind of method for preparing low impurity high power capacity ultracapacitor activated carbon Download PDF

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CN108190889A
CN108190889A CN201810252120.9A CN201810252120A CN108190889A CN 108190889 A CN108190889 A CN 108190889A CN 201810252120 A CN201810252120 A CN 201810252120A CN 108190889 A CN108190889 A CN 108190889A
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activated carbon
high power
passed
power capacity
low impurity
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王大志
张泽忠
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Beijing Hcc Energy Tech Co Ltd
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Beijing Hcc Energy Tech Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
    • Y02E60/13—Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention discloses a kind of methods for preparing low impurity high power capacity ultracapacitor activated carbon, raw material are subjected to pre-treatment, obtain carbonized material, then carbonized material is milled into powder particles, the charing feed powder after milling is added in into activator activation, obtains activated material, then by recycling intermediary, washing, dry acquisition activated carbon, gained activated carbon depth is heat-treated, obtains final products.The present invention by raw material pre-treatment, carries out preliminary charing calcining, generates the hole for being easy to that pore-creating is penetrated into activator first；Then milling, more than 500 mesh, to be dissolved out using alkali metal ion, reaches below 100ppm to 300 mesh are less than；And heat-treated by depth, the activated carbon heat-treated with hydrogen, by oxonium ion removal reducing hydrogen ions, no longer combined with oxygen, surface function after hydrogen thermal reduction is very low, reduces the organic ash content of activated carbon, reduces the generation of gas in capacitor, improves the service life of capacitor.

Description

A kind of method for preparing low impurity high power capacity ultracapacitor activated carbon
Technical field
The present invention relates to a kind of methods for preparing low impurity high power capacity ultracapacitor activated carbon, belong to ultracapacitor system Standby field.
Background technology
The rapid development of industry, motor vehicles are increasing, seriously polluted, and the body that haze serious threat people is good for Health；The mankind unlimitedly exploit, using oil, cause diposits of petroleum future exhausted, people need a kind of new material Oil is substituted, activated carbon is to work as the new energy storage material of former, and is preferable electrode energy storage material, which has material hole It flourishing, electrochemically stable, the features such as use scope is wide, pollution-free, is widely applied to the active/standby of each electronic product and uses power supply. With the application and development in electric vehicle field, the ultracapacitor automobile that energy storage material is done with activated carbon has been settled in major City is run well, and charge and discharge are fast, with environmental-friendly, tail vapour zero-emission, but actually use situation with the theoretical service life in the presence of centainly poor Away from, it is excessive etc. including loss under high power longtime running or larger, attenuation, the reason is that active carbon electrode material is still deposited In certain impurity, purity is not ideal enough, how to further improve the steady in a long-term and reliability of super capacitor, is carbon material research The important topic of worker's research.
Invention content
In order to solve the deficiencies in the prior art, low impurity high power capacity is prepared the purpose of the present invention is to provide a kind of The method of ultracapacitor activated carbon, the activated carbon impurities content prepared is low, packing density is higher, and specific capacitance is larger, resistance to Persistently, high power capacity and stability is good.
In order to achieve the above objectives, the technology used in the present invention means are：It is a kind of to prepare low impurity high power capacity super capacitor Raw material are carried out pre-treatment, obtain carbonized material, then carbonized material is milled into powder particles, will be milled by the method for device activated carbon Charing feed powder afterwards adds in activator and activates, and obtains activated material, then by recycling intermediary, washs, dry acquisition activated carbon, Gained activated carbon depth is heat-treated, obtains final products.
Further, the pre-treatment refers to：Raw material are placed in closed environment, protection gas is passed through, is warming up to 800 DEG C, 100 DEG C are then cooled to, stopping is passed through protection gas, is cooled to room temperature.
Further, it is described to be passed through protection gas, it is warming up to 800 DEG C and refers to：100 DEG C are warming up to, is passed through protection gas, is continued 600 DEG C, 700 DEG C, 800 DEG C are warming up to, and 1~2h is kept the temperature at 700 DEG C.
Further, the pre-treatment refers to：Raw material are crushed to 100 mesh, nickel boat is then fitted into and puts in tube furnace, It is closed, 100 DEG C are warming up to, is passed through N2, 600 DEG C, 700 DEG C, 800 DEG C are continuously heating to, and 1~2h is kept the temperature at 700 DEG C, then dropped For temperature to 100 DEG C, stopping is passed through N2, it is cooled to room temperature.
Further, the milling refers to：Carbonized material is milled to granularity in the mesh of 300 mesh~500.
Further, the addition activator activation refers to：Charing powder is mixed with activator, in temperature 360~400 DEG C curing, then move into closed container in, protection gas is passed through when being warming up to 120~170 DEG C, is continuously heating to 600~800 DEG C, 1~3h is kept the temperature, is cooled to 500 DEG C, stopping is passed through protection gas, obtains activated material.
Further, the recycling intermediary, washing, drying refer to：Activated material is taken out and is sprinkled water, makes intermediate product charcoal wet Profit, after cooling, is dissolved in boiling water, and the charcoal after stirring recycling carbonate solution adds hydrochloric acid solution or acetic acid solution twice respectively, will Hydrochloric acid or acetic acid solution flood charcoal face, and acid boils, and often plus a hydrochloric acid or acetic acid solution, acid boils once, a time 0.5~ 1.5h is washed with deionized to pH value neutrality, and after second wash reaches neutrality, filtering is dry in 120 DEG C of drying boxes 3h obtains high power capacity activated carbon.
Further, the depth thermal reduction, obtains final products and refers to：Gained activated carbon is packed into nickel boat, is put into 100 DEG C tube furnace in, it is closed, be passed through protection gas, H changed when being warming up to 150 DEG C2, 600~800 DEG C are warming up to, keeps the temperature 3~10h, it is cold But protection gas is changed to 150 DEG C, continues cool to room temperature, taken out, mixed up to low ash high-capacitance double layer capacitor activity Charcoal.
The beneficial effects of the invention are as follows：First by raw material pre-treatment, preliminary charing calcining is carried out, particularly 700 DEG C heat preservation makes volatility of raw material part largely be precipitated, and generates the hole for being easy to that pore-creating is penetrated into activator；Then milling is to less than 300 Mesh more than 500 mesh, to be dissolved out using alkali metal ion, reaches below 100ppm；And heat-treated by depth, with hydrogen heat also Former activated carbon, oxonium ion removal reducing hydrogen ions are no longer combined with oxygen, and the surface function after hydrogen thermal reduction is very low, It reduces the organic ash content of activated carbon, reduce the generation of gas in capacitor, improve the service life of capacitor.
Description of the drawings
The invention will be further elaborated with reference to the accompanying drawings and examples.
Fig. 1 is the flow chart of the embodiment of the present invention 1；
Fig. 2 is the constant current charge-discharge curve graph of the embodiment of the present invention 1.
Specific embodiment
Raw material are carried out pre-treatment, obtain charcoal by a kind of method for preparing low impurity high power capacity ultracapacitor activated carbon Carbonized material is then milled into powder particles by material, and the charing feed powder after milling is added in activator activation, obtains activated material, and Afterwards by recycling intermediary, gained activated carbon depth is heat-treated, obtains final products by washing, dry acquisition activated carbon.
The pre-treatment of raw material：Carbon Materials petroleum coke（The coal tar pitch of coking, the phenolic resin of coking, interphase microballoon, tree The contenting carbon materials such as lipid microspheres）It has to pass through and tentatively carbonizes calcination processing early period, to reach the capacitance that packing density is big, capacitance is high The purpose of device activated carbon, method:By taking petroleum coke does raw material as an example, it is less than 100 mesh through particle size after cracking, then by the material not It is carbonized at same temperature.
When being carbonized under 600 DEG C of inert gas protection, char-forming material volatile quantity is moderate, after fugitive constituent volatilization, carbon matrix Surface and interior surface leave a large amount of hole, and in activation process, activator is easier into the hole of material, and with The carbon ion of active site reflects to form micropore and mesoporous on hole surface；Carbonization temperature is relatively low, and charcoal graphitization crystallite has started on a small quantity It is formed, but carbon structure, still based on unordered charcoal, the active site on Carbon Materials is more, these are all conducive to priming reaction generation K2CO3、KO2, CO etc., Carbon Materials, which are etched, leaves hole.Thus, methylene blue, iodine sorption value, quality specific capacitance are all high, filling Density is relatively low.Methylene blue, iodine sorption value height are the high methylene blues premised on reducing packing density, high iodine sorption value, no But it influences packing density to improve, and have an effect on the conductivity of activated carbon, conductivity is made to become smaller, the reason is that specific surface area is bigger, Charcoal proportion in activated carbon middle hole wall is lower, and contact area becomes smaller between active carbon particle, the conductivity of activated carbon with Specific surface area increases and reduces, it is clear that improves the pack completeness in bulk density and its ultracapacitor and is conducive to improve activated carbon The conductivity of electrode, and then improve the specific capacitance and charge-discharge performance of ultracapacitor.
When being continuously heating to 700 DEG C, because also having inside Carbon Materials after 600 DEG C of charings, some fugitive constituents are non-volatile, and 700 DEG C Charing will also generate a large amount of H2, therefore, the carbonized material after 700 DEG C of charings still leaves a part of hole, is conducive to activator It penetrates into and pore-creating.In addition, carbon structure also has more unordered charcoal and active site, easily reacted with KOH, form hole.In a organized way The ratio of carbon gradually increases, and priming reaction is mild, therefore, the activated carbon that the Carbon Materials after 700 DEG C of charings are activated and prepared, methylene Base indigo plant, iodine number, packing density are higher, and quality specific capacitance, volumetric capacitance reach highest.
800 DEG C of carbonizations are continuously heating to, carbon material crystallite gradually increases, grows up, and orderly carbon increases, and disordered carbon is reduced, stone Blackization degree is higher, and aromatic ring arrangement is even closer.800 DEG C of activation, alkali metal etching power relative difficulty, methylene blue is low, Packing density is big, but specific surface area is very low, and specific capacitance is low.
Therefore, we are warming up to 800 DEG C and refer to：Be warming up to 100 DEG C, be passed through protection gas, be continuously heating to 600 DEG C, 700 DEG C, 800 DEG C, and keep the temperature 1~2h at 700 DEG C, fully give 700 DEG C of carbonization time.
With the char-forming material direct activation not being carbonized, since carbonized stock contains a large amount of fugitive constituent, these fugitive constituents are in height During temperature activation, volume contraction is larger, and activator penetration is suppressed, activated carbon methylene blue adsorption value, the iodine sorption value of preparation Low, specific capacity is reduced with methylene blue, iodine sorption value and is reduced；When fugitive constituent is high, carbon content is low, and activator is opposite to be increased, material Material structure is that amorphous randomness, active site number are more, activator the reaction of the surface of material acutely, oxidation aggravate, burn tinctuer Height causes packing density, methylene blue, iodine sorption value all relatively low.
Milling reduces inorganic ash content：
Carbonized material is milled to less than 300 mesh；More than 500 mesh, alkali metal ion content measured just easily reaches below 100ppm.
Activated carbon is activated often using alkaline earth metal compounds such as potassium hydroxide as activator, after activation, containing big in activated material The alkali metal ion of amount, these alkali metal, which must remove, reaches 100ppm hereinafter, otherwise, the activated carbon containing more potassium impurity does electricity Pole forms capacitor, and during energization, diaphragm, which is easily corroded, makes electric pole short circuit and capacitor failure.Alternatively, alkali metal ion and electricity Solution liquid, which reacts, generates salt, these salts are attached to electrode surface, barrier electrolyte ion disengaging, and internal resistance increases, and capacity subtracts It is small.Meanwhile electrolyte is decomposed and solution concentration is thinning, capacitance fall-off.Due to the presence of alkali metal, leakage current becomes larger, and fills Discharging efficiency reduces, and energy density degenerates, and self-discharge conservation rate reduces.So charing material granularity is ground to 300- by the present invention 500 mesh.The granularity of material is small, and alkali metal ion easily dissolves out, and easily reaches 100ppm hereinafter, the low charcoal of alkali metal ion content measured Material is used as electrode material, can increase substantially the resistance to persistence of capacitor；The granularity of material is smaller, with activator contact area Bigger, activation is faster；The granularity of material is smaller, and the time that activator enters material internal activation is shorter；Activity is prepared out Charcoal, activated carbon surface position will not just activate excessively and malformation, hole caused to collapse；The granularity of material is smaller, activated carbon Internal potassium ion is nearer away from activated carbon surface, the easier dissolution of alkali metal ion；Moreover the time of activation is shorter, alkali metal Ion generate chemical bond is relatively fewer, acid boils, wash after, potassium ion easily reaches within 100ppm.But too low grain size Also carbon material can be caused to be easy to the problem of ablation is so as to bring low-density, preferred size is less than 300 mesh.
Hydrogen heat-treats, and reduces organic impurities：
Surface functional group is the most organic impurities of activated carbon content, needs to be down to functional group with optimum time and temperature It is minimum.Activated carbon is the core material of ultracapacitor, either Physical or the activated carbon of chemical method preparation, surface All there is the oxygen-containing functional groups combined with carbon phase, due to the presence of surface functional group, are assembled into capacitor energization long-term work Shi Huiyu electrolyte collective effect and generate CO, CO2Gases are waited, which increase pressure in capacitor, gradually generate heat, is swollen It is swollen, internal resistance is caused to increase, malformation, capacitance fall-off are accelerated；Make electrolyte decomposition and influence the raising of voltage, surface function Carboxyl in group with directly affecting capacitor storge quality, carboxyl-content is more, and leakage current is bigger；Due to depositing for surface functional group In prolonged charge and discharge process, carbon electrode material generates gas and bubbling, and electrode Carbon Materials are removed with collector, are reduced The area of charge is formed, makes the capacity of capacitor reduce, speed-up capacitor device fails；Extend the service life of capacitor, increase Add resistance to persistence, it is necessary to the surface functional group of removal carbon electrode material as much as possible.The present invention is heat-treated using hydrogen, by charcoal Nickel boat is packed into, is put into 100 DEG C of tube furnace, it is closed, it is passed through N2Heating, 150 DEG C are changed H2, handled in different temperature and times Afterwards, 150 DEG C are cooled to and changes N2, until room temperature（The medium temperature of container）, it takes out, mixes to get to low surface functional group activated carbon, It is minimum to reach 0.23mmol/L.
There are two ways to the prior art generally goes to capacitor activated carbon surface official group：（1）High temperature smoldering method,（2）Inert Gas protection method, both methods can remove oxygen-containing function functional group in high temperature furnace, but after coming out of the stove, and being contacted with oxygen can also generate Part surface functional group, using both the above method, treated that capacitor activated carbon surface functional group rests on 0.6mmol/g, And the activated carbon of the application thermal reduction, oxonium ion removal reducing hydrogen ions are not combined with oxygen.So after hydrogen thermal reduction Surface function it is very low, reduce the organic ash content of activated carbon, reduce the generation of gas in capacitor, improve longevity of capacitor Life.
Embodiment 1
As shown in Figure 1, a kind of method for preparing low impurity high power capacity ultracapacitor activated carbon, comprises the steps of：
1-1, charing：By petroleum coke 200g particle size after cracking to 100 mesh, 100g is weighed, nickel boat is packed into and puts tube furnace, 100 DEG C are passed through N2, it is closed, after continuing 700 DEG C of heating, 1.5h is kept the temperature, 100 DEG C is cooled to and stops N2To room temperature, test is taken out；Volatile matter 7%；
1-2, milling：The carbonized stock of charing is milled, granularity is less than 300 mesh（Pass through 300 the polished standard screens）, take out, mixing；
1-3, activation：Weigh milling material 20g and activator 80g（Alkali carbon ratio 4：1）Together, it in 400 DEG C of curings of temperature, moves nickel boat and enters Tube furnace, closed, 150 DEG C are passed through N2, 800 DEG C are warming up to, keeps the temperature 2 hours, is cooled to 500 DEG C, closes nitrogen, is taken out, is spilt a small amount of Water, make intermediate product charcoal moisten, after cooling, be dissolved in the boiling water of 500ml beakers, stir；
1-4, acid are boiled, are washed：Intermediate product charcoal is added into 1mmol/L hydrochloric acid solutions twice respectively, hydrochloric acid solution is made to flood charcoal face, often Add a hydrochloric acid solution, acid boils once（1h）, with deionized water, washed several times with water to pH value reaches neutral, and the second hypo acid boils（1h）, After washing reaches neutrality, when chemical examination is qualified, filtering, dry 3h heat-treats embodiment 1 to get unreacted hydrogen gas in 120 DEG C of drying boxes Carbon sample；
1-5、H2Depth heat-treats：Charcoal is packed into nickel boat, is put into 100 DEG C of tube furnace, it is closed, it is passed through N2, heating, 150 DEG C Change H2, after being warming up to 700 DEG C of heat preservation 8h, it is cooled to 150 DEG C and changes N2, until room temperature（The medium temperature of container）, take out, mix to get To low ash high-capacitance double layer capacitor activated carbon.
Through analysis:Low ash high-capacitance double layer capacitor activated carbon.Methylene blue adsorption value 42ml, iodine number This charcoal is done electricity by 2549mg/g, packing density 0.46g/ml, potassium 52ppm surface functional group 0.23mmmol/L, ash 0.054% Pole is assembled into double layer capacitor, is 5mA/g in constant current charge-discharge, charging voltage 2.7V is electrolysis with 1M Et4NBF4/PC Liquid, after 10 cycles, quality specific capacitance 185.5F/g, energy density 47Wh/kg, after 10000 cycles of charge and discharge, mass ratio electricity Hold 170.7F/g, conservation rate 92%.
Comparative example 2
2-1, raw material：Petroleum coke, comparative example 2-1 are not carbonized, and former 100 mesh of coking crushes material；
2-2, comparative example 2-2 are identical with embodiment 1-2 conditions；
2-3, comparative example 2-3 are identical with embodiment 1-3 conditions；
2-4, comparative example 2-4 are identical with embodiment 1-4 conditions；
2-5、H2Depth heat-treats：Charcoal is packed into nickel boat, is put into 100 DEG C of tube furnace, it is closed, it is passed through N2, heating, 150 DEG C Change H2, after being warming up to 700 DEG C of heat preservation 8h, it is cooled to 150 DEG C and changes N2, until room temperature（The medium temperature of container）, take out, mix to get To 2 carbon sample of comparative example.
Through analysis；Methylene blue adsorption value 28ml, iodine number 1608mg/g, packing density 0.37g/ml, ash 0.074%, potassium 80ppm, surface functional group 0.27mmol/L；This charcoal is done into electrode assembling into double layer capacitor, is 5mA/ in constant current charge-discharge G, charging voltage 2.7V are electrolyte with 1M Et4NBF4/PC, after 10 times recycle, quality specific capacitance 131F/g, and energy density 33.2Wh/kg, after the cycle of charge and discharge 10000 times, quality specific capacitance 117.9F/g, conservation rate 90%.
Comparative example 3
3-1, raw material：Petroleum coke, comparative example 3-1 are differed with embodiment 1-1 carburizing temperatures, 600 DEG C of carburizing temperature；
3-2, comparative example 3-2 and embodiment 1-2, condition are identical；
3-3, comparative example 3-3 and embodiment 1-3, condition are identical；
3-4, comparative example 3-4) with embodiment 1-4, condition is identical；
3-5、H2Depth heat-treats：Charcoal is packed into nickel boat, is put into 100 DEG C of tube furnace, it is closed, it is passed through N2, heating, 150 DEG C Change H2, after being warming up to 700 DEG C of heat preservation 8h, it is cooled to 150 DEG C and changes N2, until room temperature（The medium temperature of container）, take out, mix to get To 3 carbon sample of comparative example.
Through analysis：Methylene blue adsorption value 36ml, iodine number 2423mg/g, packing density 0.38g/ml, ash 0.053%, potassium 68ppm, iron 0.002%, chlorine 0.003%, surface functional group 0.25mmol/L, pH value 7；This charcoal is done into electrode assembling into electric double layer electricity Container is 5mA/g, charging voltage 2.7V in constant current charge-discharge, is electrolyte with 1M Et4NBF4/PC, after 10 times recycle, matter Measure specific capacitance 152F/g, energy density 38.5Wh/kg, after the cycle of charge and discharge 10000 times, quality specific capacitance 136.8F/g is kept Rate 90%.
Comparative example 4
4-1, raw material：Petroleum coke, comparative example 4-1 are differed with embodiment 1-1 carburizing temperatures, 800 DEG C of carburizing temperature；
4-2, comparative example 4-2 are identical with embodiment 1-2 conditions；
4-3, comparative example 4-3 are identical with embodiment 1-3 conditions；
4-4, comparative example 4-4 are identical with embodiment 1-4 conditions；
4-5、H2Depth heat-treats：Charcoal is packed into nickel boat, is put into 100 DEG C of tube furnace, it is closed, it is passed through N2, heating, 150 DEG C Change H2, after being warming up to 700 DEG C of heat preservation 8h, it is cooled to 150 DEG C and changes N2, until room temperature（The medium temperature of container）, take out, mix to get To 4 carbon sample of comparative example.Through analysis：Methylene blue adsorption value 24ml, iodine number 1586mg/g, packing density 0.51g/ml, ash This charcoal is done electrode assembling into double layer capacitor, in constant current charge and discharge by 0.062%, potassium 74ppm, surface functional group 0.24mmol/L Electricity is 5mA/g, charging voltage 2.7V, is electrolyte with 1MEt4NBF4/PC, after 10 times recycle, quality specific capacitance 128F/g, Energy density 32.4Wh/kg, after the cycle of charge and discharge 10000 times, quality specific capacitance 117.8F/g, conservation rate 92%.
Analyze embodiment 1, comparative example 2,3,4, the different quality of activated carbon table such as 1 carburizing temperature of table
。
Comparative example 5
5-1, raw material：Petroleum coke, comparative example 5-1 are identical with embodiment 1-1 conditions；
5-2, comparative example 5-2 are different from embodiment 1-2, and granularity is 150 mesh；
5-3, comparative example 5-3 are identical with embodiment 1-3 conditions；
5-4, comparative example 5-4 are identical with embodiment 1-4 conditions；
5-5、H2Depth heat-treats：Charcoal is packed into nickel boat, is put into 100 DEG C of tube furnace, it is closed, it is passed through N2, heating, 150 DEG C Change H2, after being warming up to 700 DEG C of heat preservation 8h, it is cooled to 150 DEG C and changes N2, until room temperature（The medium temperature of container）, take out, mix to get To 5 carbon sample of comparative example.
Through analysis：Methylene blue adsorption value 37ml, iodine number 2484mg/g, packing density 0.47g/ml, ash 0.18%, iron 0.003%, chlorine 0.002, surface functional group 0.27mmol/L, pH value 7, potassium ion 0.427ppm；It is in pairs that this charcoal is done into electrode assembling Electric layer capacitor is 5mA/g, charging voltage 2.7V in constant current charge-discharge, is electrolyte with 1M Et4NBF4/PC, follows for 10 times After ring, quality specific capacitance 176.2F/g, energy density 44.6Wh/kg, after 10000 cycles of charge and discharge, quality specific capacitance 132.2F/g conservation rate 75%.Stream charge and discharge are 5mA/g, and charging voltage 2.7V uses 1MEt.
Comparative example 6
6-1, raw material：Petroleum coke, comparative example 6-1 are identical with embodiment 1-1 conditions；
6-2, comparative example 6-2 and embodiment 1-2 conditions differ, 200 mesh of viscosity；
6-3, comparative example 6-3 are identical with embodiment 1-3 conditions；
6-4, comparative example 6-4 are identical with embodiment 1-4 conditions；
6-5、H2Depth heat-treats：Charcoal is packed into nickel boat, is put into 100 DEG C of tube furnace, it is closed, it is passed through N2, heating, 150 DEG C Change H2, after being warming up to 700 DEG C of heat preservation 8h, it is cooled to 150 DEG C and changes N2, until room temperature（The medium temperature of container）, take out, mix to get To 6 carbon sample of comparative example.
Through analysis：Methylene blue adsorption value 39ml, iodine number 2498mg/g, packing density 0.39g/ml, ash 0.12%, table Face functional group 0.26mmol/L, potassium ion 253ppm；This charcoal is done into electrode assembling into double layer capacitor, is in permanent 4NBF4/PC Electrolyte, after 10 cycles, quality specific capacitance 180F/g, energy density 45.6Wh/kg, after 10000 cycles of charge and discharge, quality Specific capacitance 144F/g, conservation rate 80%.
Comparative example 7
7-1, raw material：Petroleum coke, comparative example 7-1 are identical with embodiment 1-1 conditions；
7-2, comparative example 7-2 and embodiment 1-2 conditions differ, 500 mesh of granularity；
7-3, comparative example 7-3 are identical with embodiment 1-3 conditions；
7-4, comparative example 7-4 are identical with embodiment 1-4 conditions；
7-5、H2Depth heat-treats：Charcoal is packed into nickel boat, is put into 100 DEG C of tube furnace, it is closed, it is passed through N2, heating, 150 DEG C Change H2, after being warming up to 700 DEG C of heat preservation 8h, it is cooled to 150 DEG C and changes N2, until room temperature（The medium temperature of container）, take out, mix to get To 7 carbon sample of comparative example.
Through analysis：Methylene blue adsorption value 40ml, iodine number 2495mg/g, packing density 0.39g/ml, ash 0.047%, table Face functional group 0.27mmol/L, potassium ion 56ppm；This charcoal is done into electrode assembling into double layer capacitor, is in permanent 4NBF4/PC Electrolyte, after 10 cycles, quality specific capacitance 178.7F/g, energy density 45.2Wh/kg, after 10000 cycles of charge and discharge, matter Measure specific capacitance 157.3F/g, conservation rate 88%.
Embodiment 1 and comparative example 5,6,7 are analyzed, such as the granularity different activities carbonaceous scale of 2 carbonized stock of table
。
Comparative example 8
8-1, raw material：Petroleum coke, comparative example 8-1 are identical with embodiment 1-1 conditions；
8-2, comparative example 8-2 are identical with embodiment 1-2 conditions；
8-3, comparative example 8-3 are identical with embodiment 1-3 conditions；
8-4, comparative example 8-4 are identical with embodiment 1-4 conditions；
8-5、H2Depth heat-treats and embodiment 1-5, H2The depth thermal reduction time is different；H2The depth thermal reduction time is 4 hours, Other conditions are identical.
8-4 carbon samples are packed into nickel boat, are put into 100 DEG C of tube furnace, it is closed, N2 is passed through, is heated up, 150 DEG C are changed H2, heating To 700 DEG C of heat preservation 4h, it is cooled to 150 DEG C and changes N2, until room temperature（The medium temperature of container）, take out, mix to get to comparative example 8 carbon samples.
Through analysis；Packing density 0.45g/ml, ash 0.05%, surface functional group 0.35mmol/L. potassium ions 50ppm.It will This charcoal does electrode assembling into double layer capacitor, is 5mA/g, charging voltage 2.7V in constant current charge-discharge, with 1M Et4NBF4/ PC is electrolyte, after 10 times recycle, after 10000 cycles of quality specific capacitance 188F/g charge and discharge, and conservation rate 84%.
Comparative example 9
9-1, raw material：Petroleum coke, comparative example 9-1 are identical with embodiment 1-1 conditions；
9-2, comparative example 9-2 are identical with embodiment 1-2 conditions；
9-3, comparative example 9-3 are identical with embodiment 1-3 conditions；
9-4, comparative example 9-4 are identical with embodiment 1-4 conditions；
9-5、H2Depth thermal reduction is differed with embodiment 1-5 conditions, H2Depth heat also time 9h.
9-5 carbon samples are packed into nickel boat, are put into 100 DEG C of tube furnace, it is closed, it is passed through N2, heating, 150 DEG C are changed H2, heating To 700 DEG C of heat preservation 4h, it is cooled to 150 DEG C and changes N2, until room temperature（The medium temperature of container）, take out, mix to get to comparative example 9 carbon samples.
Through analysis：Surface functional group 0.23mmol/L, packing density 0.46g/ml, ash 0.055%, potassium ion 60ppm. This charcoal is done into electrode assembling into double layer capacitor, is 5mA/g in constant current charge-discharge, charging voltage 2.7V uses 1M Et4NBF4/PC is electrolyte, and after 10 times recycle, quality specific capacitance 179F/g charges 10000 times after recycling, conservation rate 92%.
Comparative example 10
10-1, raw material：Petroleum coke, comparative example 10-1 are identical with embodiment 1-1 conditions；
10-2, comparative example 10-2 are identical with embodiment 1-2 conditions；
10-3, comparative example 10-3 are identical with embodiment 1-3 conditions；
10-4, comparative example 10-4 are identical with embodiment 1-4 conditions；
10-5、H2Depth thermal reduction is differed with embodiment 1-5 conditions, H2Depth heat also 800 DEG C of temperature, time 8h.By 10-5 Carbon sample is packed into nickel boat, is put into 100 DEG C of tube furnace, closed, is passed through N2, heating, 150 DEG C are changed H2, it is warming up to 800 DEG C of heat preservation 8h Afterwards, 150 DEG C are cooled to and changes N2, until room temperature（The medium temperature of container）, take out, mix to get to 10 carbon sample of comparative example.
Through analysis；Surface functional group 0.23mmol/L, packing density 0.47g/ml, ash 0.057%, potassium ion 62ppm. This charcoal is done into electrode assembling into double layer capacitor, is 5mA/g in constant current charge-discharge, charging voltage 2.7V uses 1M Et4NBF4/PC is electrolyte, and after 10 times recycle, quality specific capacitance 164F/g charges 10000 times after recycling, conservation rate 91%.
Comparative example 1 and comparative example 8,9,10 obtain quality of activated carbon table after the processing of 3 temperature and time difference hydrogen of table
。
More than ten cases, the quality of activated carbon that embodiment 1 is prepared is best, and impurity content is low, packing density is big, capacitance Amount is high, and preparation method is exactly implemented according to the invention：1st, 700 DEG C of carbonizations of carbonized stock, capacitance, packing density are carried It is high；2nd, it is surface functional group granularity is levigate, until 300 mesh, drop to 52ppm, ash content reaches 0.054%, makes capacitor by alkali metal Capacitance fall-off become smaller；Surface functional group is preferably minimized by the 3rd, hydrogen thermal reduction, is reached 0.23mmol/l, is improved capacitor The conservation rate and durability of capacitance.
1 carbon sample of embodiment does carbon resistance rod, is assembled into button simulation double layer capacitor, is 5mA/g in constant current charge-discharge, fills Piezoelectric voltage is 2.7V, is electrolyte with 1M Et4NBF4/PC, after 10 times recycle, quality specific capacitance 185.5F/g, and energy density 47Wh/kg, after the cycle of charge and discharge 10000 times, quality specific capacitance 170.7F/g, conservation rate 92%, as shown in Fig. 2, cycle 10000 Secondary most latter two constant current charge-discharge curve graph.
One of ordinary skill in the art will appreciate that：The above embodiments are only used to illustrate the technical solution of the present invention., and It is non-that it is limited；Although the present invention is described in detail with reference to foregoing embodiments, those of ordinary skill in the art It should be understood that：It can still modify to the technical solution recorded in foregoing embodiments either to which part or All technical features carries out equivalent replacement；And it these modifications or replaces, it does not separate the essence of the corresponding technical solution this hair The range of bright each embodiment technical solution.

Claims (8)

  1. A kind of 1. method for preparing low impurity high power capacity ultracapacitor activated carbon, it is characterised in that：Locate before raw material are carried out Reason obtains carbonized material, and then carbonized material is milled into powder particles, and the charing feed powder after milling is added in activator activation, is obtained Activated material, then by recycling intermediary, gained activated carbon depth is heat-treated, obtained final by washing, dry acquisition activated carbon Product.
  2. 2. the method according to claim 1 for preparing low impurity high power capacity ultracapacitor activated carbon, it is characterised in that：Institute Pre-treatment is stated to refer to：Raw material are placed in closed environment, are passed through protection gas, are warming up to 800 DEG C, 100 DEG C is then cooled to, stops Protection gas is only passed through, is cooled to room temperature.
  3. 3. the method according to claim 2 for preparing low impurity high power capacity ultracapacitor activated carbon, it is characterised in that：Institute It states and is passed through protection gas, be warming up to 800 DEG C and refer to：Be warming up to 100 DEG C, be passed through protection gas, be continuously heating to 600 DEG C, 700 DEG C, 800 DEG C, and keep the temperature 1~2h at 700 DEG C.
  4. 4. the method according to claim 1 for preparing low impurity high power capacity ultracapacitor activated carbon, it is characterised in that：Institute Pre-treatment is stated to refer to：Raw material are crushed to 100 mesh, nickel boat is then fitted into and puts in tube furnace, it is closed, 100 DEG C are warming up to, is passed through N2, 600 DEG C, 700 DEG C, 800 DEG C are continuously heating to, and 1~2h is kept the temperature at 700 DEG C, are then cooled to 100 DEG C, stopping is passed through N2, It is cooled to room temperature.
  5. 5. the method according to claim 1 for preparing low impurity high power capacity ultracapacitor activated carbon, it is characterised in that：Institute Milling is stated to refer to：Carbonized material is milled to granularity in the mesh of 300 mesh~500.
  6. 6. the method according to claim 1 for preparing low impurity high power capacity ultracapacitor activated carbon, it is characterised in that：Institute It states to add in activator and activate and refer to：Charing powder with activator is mixed, in 360~400 DEG C of curings of temperature, is then moved into closed In container, protection gas is passed through when being warming up to 120~170 DEG C, is continuously heating to 600~800 DEG C, 1~3h is kept the temperature, is cooled to 500 DEG C, stopping is passed through protection gas, obtains activated material.
  7. 7. the method according to claim 1 for preparing low impurity high power capacity ultracapacitor activated carbon, it is characterised in that：Institute Recycling intermediary is stated, washing, drying refer to：Activated material is taken out and is sprinkled water, intermediate product charcoal is moistened, after cooling, is dissolved in boiling water In, the charcoal after stirring recycling carbonate solution adds hydrochloric acid solution or acetic acid solution twice, hydrochloric acid or acetic acid solution is flooded respectively Charcoal face, acid boil, and often plus a hydrochloric acid or acetic acid solution, acid boils once, and a time in 0.5~1.5h, is washed with deionized To pH value neutrality, after second wash reaches neutrality, filtering, dry 3h, obtains high power capacity activated carbon in 120 DEG C of drying boxes.
  8. 8. the method according to claim 1 for preparing low impurity high power capacity ultracapacitor activated carbon, it is characterised in that：Institute Depth thermal reduction is stated, final products is obtained and refers to：Gained activated carbon is packed into nickel boat, is put into 100 DEG C of tube furnace, it is closed, Protection gas is passed through, H is changed when being warming up to 150 DEG C2, 600~800 DEG C are warming up to, 3~10h is kept the temperature, is cooled to 150 DEG C and changes protection gas, Room temperature is continued cool to, is taken out, is mixed up to low ash high-capacitance double layer capacitor activated carbon.
CN201810252120.9A 2018-03-26 2018-03-26 A kind of method for preparing low impurity high power capacity ultracapacitor activated carbon Pending CN108190889A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109592681A (en) * 2019-01-25 2019-04-09 浙江大学 A kind of preparation of industrialization of coconut husk super capacitor highly pure active charcoal purification process step by step
CN109850892A (en) * 2019-01-25 2019-06-07 浙江大学 A kind of activation industrialized process for preparing twice of super capacitor high conductivity cocoanut active charcoal
CN109928392A (en) * 2019-05-08 2019-06-25 哈尔滨理工大学 A kind of preparation based on biomass carbon electrode material for super capacitor derived from elm money
CN110697712A (en) * 2019-11-27 2020-01-17 天津合众汇能科技有限公司 Preparation method of low-ash-content double-electric-layer capacitor activated carbon and capacitor
CN111943192A (en) * 2020-08-24 2020-11-17 太原理工大学 Preparation method of carbon material for supercapacitor, carbon material and application of carbon material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020039275A1 (en) * 2000-07-04 2002-04-04 Jeol Ltd., Electric double-layer capacitor and carbon material therefor
CN104401992A (en) * 2014-10-22 2015-03-11 深圳市贝特瑞新能源材料股份有限公司 Method for preparing activated carbon for super capacitor with fruit shells as raw material and application of activated carbon
CN104817082A (en) * 2015-05-22 2015-08-05 安徽工业大学 Method for preparing nitrogen-enriched porous carbon material for supercapacitor by taking lignite as raw material
CN107043109A (en) * 2017-04-07 2017-08-15 南京正森环保科技有限公司 A kind of preparation method of starch based super electric capacity absorbent charcoal material
CN107804848A (en) * 2017-11-21 2018-03-16 浙江省林业科学研究院 A kind of preparation method of the straw base porous activated carbon of surface active

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020039275A1 (en) * 2000-07-04 2002-04-04 Jeol Ltd., Electric double-layer capacitor and carbon material therefor
CN104401992A (en) * 2014-10-22 2015-03-11 深圳市贝特瑞新能源材料股份有限公司 Method for preparing activated carbon for super capacitor with fruit shells as raw material and application of activated carbon
CN104817082A (en) * 2015-05-22 2015-08-05 安徽工业大学 Method for preparing nitrogen-enriched porous carbon material for supercapacitor by taking lignite as raw material
CN107043109A (en) * 2017-04-07 2017-08-15 南京正森环保科技有限公司 A kind of preparation method of starch based super electric capacity absorbent charcoal material
CN107804848A (en) * 2017-11-21 2018-03-16 浙江省林业科学研究院 A kind of preparation method of the straw base porous activated carbon of surface active

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109592681A (en) * 2019-01-25 2019-04-09 浙江大学 A kind of preparation of industrialization of coconut husk super capacitor highly pure active charcoal purification process step by step
CN109850892A (en) * 2019-01-25 2019-06-07 浙江大学 A kind of activation industrialized process for preparing twice of super capacitor high conductivity cocoanut active charcoal
CN109592681B (en) * 2019-01-25 2020-06-16 浙江大学 Industrial preparation step-by-step purification method of coconut shell super-capacitor high-purity activated carbon
CN109928392A (en) * 2019-05-08 2019-06-25 哈尔滨理工大学 A kind of preparation based on biomass carbon electrode material for super capacitor derived from elm money
CN110697712A (en) * 2019-11-27 2020-01-17 天津合众汇能科技有限公司 Preparation method of low-ash-content double-electric-layer capacitor activated carbon and capacitor
CN111943192A (en) * 2020-08-24 2020-11-17 太原理工大学 Preparation method of carbon material for supercapacitor, carbon material and application of carbon material

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