CN103682345A - Carbon-based electrode material, preparation method of carbon-based electrode material and energy storage device - Google Patents
Carbon-based electrode material, preparation method of carbon-based electrode material and energy storage device Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a carbon-based electrode material, a preparation method of the carbon-based electrode material and an energy storage device. The preparation method of the carbon-based electrode material comprises the following steps: a) performing heat treatment on pine needles in an inert atmosphere to obtain a first carbon-based electrode material; b) mixing the first carbon-based electrode material obtained in the step a) with an alkaline substance to obtain a mixture; and c) chemically activating the mixture obtained in the step b) under an insert atmosphere to obtain a second carbon-based electrode material. According to the preparation method of the carbon-based electrode material, the pine needles are adopted as a raw material, so that the raw material is cheap and available; the first carbon-based electrode material can be obtained by performing heat treatment on the pine needles; the obtained first carbon-based material is mixed with the alkaline substance and then chemically activated to obtain the second carbon-based electrode material. The preparation method of the carbon-based electrode material is simple in step, easily-controllable in operation process, low in energy consumption and applicable to the needs of industrial production. The carbon-based electrode material can serve as an electrode of the energy storage device.
Description
Technical field
The present invention relates to energy storage material technical field, relate in particular to a kind of application for carbon-based electrode material, its preparation method and energy storage device.
Background technology
Along with the exhaustion of petroleum resources and going from bad to worse of environment, people more and more pay close attention to the development and utilization of green energy resource.Wind energy, solar energy and water can etc. be the representative of these novel renewable energy, yet the output of these energy depends on natural conditions consumingly, and energy requirement do not mate, and therefore needs an energy storage system.When energy is unnecessary, energy storage system is stored, and can make it again to discharge when demand.In various energy storage systems, electrical power storage system plays vital effect, and for example battery and electrochemical capacitor have become the requisite energy storage device of modern society.These energy storage devices have huge using value and market potential in various fields such as electric automobile, fuel combination automobile, electric power, railway, communication, national defence, consumption electronic products, by countries in the world institute extensive concern.
Since the eighties in last century, various novel high secondary batteries come out gradually, and lithium ion battery, fuel cell etc. becomes the new power of electric automobile gradually.Compare the advantage such as lithium ion battery has that voltage is high, specific energy is high, has extended cycle life, memory-less effect, environmental pollution are little, quick charge, self-discharge rate are low with other rechargeable batteries.Lithium ion battery is considered to the choosing of the ideal of high power capacity, high power battery.For another example the sodium-ion battery growing up in order to make up the deficiency of lithium resource, also receives everybody concern gradually.Electrochemical capacitor is the novel energy-storing device growing up on traditional electrolytic capacitor, owing to having adopted novel electrode material and electrolyte system, the energy density of electrochemical capacitor has broken through the restriction of traditional capacitor microfarad range, approach 1/10th of secondary cell, and power density is the decades of times of battery, its capacity can reach hundreds of to thousands of farads, the ability with higher storage electric charge, and it is fast to have the speed of discharging and recharging, efficiency is high, environmentally safe, have extended cycle life, serviceability temperature wide ranges, the features such as fail safe height, the blank between traditional capacitor and secondary cell has been filled up in its appearance.
These energy storage devices are if lithium ion battery, sodium-ion battery and electrochemical capacitor are by electrode (active material), electrolyte, barrier film, binding agent and shell composition, wherein electrode is the core of energy storage device, by active material and the main city of conducting matrix grain, both positive and negative polarity active material is the source that produces electric energy, is the important component part that determines battery fundamental characteristics.Material with carbon element because it is cheap and easy to get, operating temperature range is wide, specific area is controlled, pore structure is flourishing, chemical stability is high, also comparative maturity, the advantage such as environmentally friendly are widely used in preparing electrode material to production technology.Preparation for carbon-based electrode material in prior art mainly contains chemical vapour deposition technique, template and high temperature pyrolysis etc., yet these method steps are loaded down with trivial details, process is complicated.
Summary of the invention
The object of the present invention is to provide a kind of carbon-based electrode material, its preparation method and energy storage device.The preparation method of carbon-based electrode material provided by the invention is simple, and the carbon-based electrode material obtaining has good chemical property.
The preparation method who the invention provides a kind of carbon-based electrode material, comprises the following steps:
A) pine needle is heat-treated under inert atmosphere, obtain the first carbon-based electrode material;
B) the first carbon-based electrode material described step a) being obtained mixes with alkaline matter, obtains mixture;
C) mixture described step b) being obtained carries out chemical activation under inert atmosphere, obtains the second carbon-based electrode material.
Preferably, the heat treatment temperature of described step a) is 400 ℃ ~ 1500 ℃;
The heat treatment time of described step a) is 2 hours ~ 12 hours.
Preferably, the alkaline matter in described step b) is hydroxide, carbonate or bicarbonate.
Preferably, the mass ratio of described step b) neutral and alkali material and the first carbon-based electrode material is (1 ~ 16): 1.
Preferably, the temperature of the chemical activation of described step b) is 800 ℃ ~ 1000 ℃;
The time of the chemical activation of described step c) is 2 hours ~ 12 hours.
The invention provides a kind of carbon-based electrode material being obtained by preparation method described in technique scheme.
The invention provides a kind of energy storage device, it is characterized in that, electrode is formed by the carbon-based electrode material described in technique scheme.
Preferably, described energy storage device is lithium rechargeable battery, and described electrode is anodal.
Preferably, described energy storage device is sodium-ion battery, and described electrode is anodal.
Preferably, described energy storage device is electrochemical capacitor.
The invention provides a kind of carbon-based electrode material, its preparation method and energy storage device.The preparation method of carbon-based electrode material provided by the invention comprises the following steps: a) pine needle is heat-treated under inert atmosphere, obtain the first carbon-based electrode material; B) the first carbon-based electrode material described step a) being obtained mixes with alkaline matter, obtains mixture; C) mixture described step b) being obtained carries out chemical activation under inert atmosphere, obtains the second carbon-based electrode material.Preparation method provided by the invention be take pine needle as raw material, and abundant raw material can obtain the first carbon-based electrode material by pine needle through Overheating Treatment; After the first carbon-based material obtaining is mixed with alkaline matter, carry out chemical activation, can obtain the second carbon-based electrode material.Method step provided by the invention is simple, and operating process is easy to control, and energy consumption is little, is suitable for industrial needs; And raw material is cheap and easy to get, thereby make preparation method provided by the invention there is lower cost.And the carbon-based electrode material that preparation method of the present invention obtains has higher ratio electric capacity, specific area is little, have extended cycle life, can be as the electrode of energy storage device.Experimental result shows, carbon-based electrode material provided by the invention, when as lithium ion secondary battery positive electrode, sodium-ion battery positive pole and electrochemical capacitor electrode, has higher specific capacity and cycle performance preferably.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the first carbon-based electrode material of obtaining of the embodiment of the present invention 1;
Fig. 2 is BJH graph of pore diameter distribution and the N of the first carbon-based electrode material of obtaining of the embodiment of the present invention 1
2adsorption-desorption isothermal linearity curve;
Fig. 3 is the SEM figure of the first carbon-based electrode material of obtaining of the embodiment of the present invention 2;
Fig. 4 is BJH graph of pore diameter distribution and the N of the first carbon-based electrode material of obtaining of the embodiment of the present invention 2
2adsorption-desorption isothermal linearity curve;
Fig. 5 is the SEM figure of the first carbon-based electrode material of obtaining of the embodiment of the present invention 3;
Fig. 6 is the SEM figure of the first carbon-based electrode material of obtaining of the embodiment of the present invention 4;
Fig. 7 is the SEM figure of the second carbon-based electrode material of obtaining of the embodiment of the present invention 4;
Fig. 8 is BJH graph of pore diameter distribution and the N of the first carbon-based electrode material of obtaining of the embodiment of the present invention 4
2adsorption-desorption isothermal linearity curve;
Fig. 9 is BJH graph of pore diameter distribution and the N of the second carbon-based electrode material of obtaining of the embodiment of the present invention 4
2adsorption-desorption isothermal linearity curve;
Figure 10 is the SEM figure of the first carbon-based electrode material of obtaining of the embodiment of the present invention 5;
Figure 11 is the SEM figure of the first carbon-based electrode material of obtaining of the embodiment of the present invention 6;
Figure 12 is the SEM figure of the second carbon-based electrode material of obtaining of the embodiment of the present invention 6;
Figure 13 is BJH graph of pore diameter distribution and the N of the first carbon-based electrode material of obtaining of the embodiment of the present invention 6
2adsorption-desorption isothermal linearity curve;
Figure 14 is BJH graph of pore diameter distribution and the N of the second carbon-based electrode material of obtaining of the embodiment of the present invention 6
2adsorption-desorption isothermal linearity curve;
Figure 15 is the specific capacity curve chart of the lithium ion battery that obtains of the embodiment of the present invention 7 ~ 12;
Figure 16 is the cycle charge-discharge curve of the lithium ion battery that obtains of the embodiment of the present invention 13;
Figure 17 is the specific capacity curve chart of the sodium-ion battery that obtains of the embodiment of the present invention 14 ~ 19;
Figure 18 is the cycle charge-discharge curve of the sodium-ion battery that obtains of the embodiment of the present invention 20;
Figure 19 is that the three-electrode system that the embodiment of the present invention 21 obtains is swept the cyclic voltammogram under speed in difference;
Figure 20 be the electrochemical capacitor that obtains of the embodiment of the present invention 22 ~ 27 sweep speed-than capacitance relation figure;
Figure 21 is the specific capacity curve chart of the symmetric form electrochemical capacitor that obtains of the embodiment of the present invention 28 ~ 29.
Embodiment
The preparation method who the invention provides a kind of carbon-based electrode material, comprises the following steps:
A) pine needle is heat-treated under inert atmosphere, obtain the first carbon-based electrode material;
B) the first carbon-based electrode material described step a) being obtained mixes with alkaline matter, obtains mixture;
C) mixture described step b) being obtained carries out chemical activation under inert atmosphere, obtains the second carbon-based electrode material.
The present invention be take pine needle as raw material, obtains the first carbon-based electrode material after being heat-treated; After the first carbon-based electrode material obtaining is mixed with alkaline matter, carry out chemical activation, obtain the second carbon-based electrode material.The original source of method provided by the invention is abundant, and preparation process is simple, be easy to control, and the carbon-based electrode material obtaining has good chemical property.Experimental result shows, carbon-based electrode material provided by the invention, when as lithium ion secondary battery positive electrode, sodium-ion battery positive pole and electrochemical capacitor electrode, has higher specific capacity and cycle performance preferably.
The present invention heat-treats pine needle under inert atmosphere, obtains the first carbon-based electrode material.In order to improve the purity of the carbon-based electrode material obtaining and to be beneficial to heat treated carrying out, the present invention preferably cleans and dries before pine needle is heat-treated, and detailed process is:
Pine needle is cleaned, obtain clean pine needle;
Described clean pine needle is dried, obtain the pine needle of drying.
In the present invention, in order to adapt to the needs of sustainable development, the fallen leaves of preferred acquisition pine tree are used as the source of pine needle.Obtain after pine needle, the present invention cleans described pine needle, obtains clean pine needle.In the present invention, described cleaning is preferably carried out according to following process: after pine needle is washed, carry out first ultrasonic; Ultrasonic by carry out again second after the first ultrasonic pine needle cleans with organic solvent; By cleaning through the second ultrasonic pine needle water, obtain clean pine needle.The present invention does not have special restriction to described first ultrasonic and the second ultrasonic method, adopt ultrasonic technical scheme well known to those skilled in the art, in the present invention, described the first ultrasonic time is preferably 5 minutes ~ and 30 minutes, more preferably 10 minutes ~ 20 minutes; Described the second ultrasonic time is preferably 5 minutes ~ and 30 minutes, more preferably 10 minutes ~ 20 minutes, described first ultrasonic time and described second ultrasonic time can be the same or different; Described organic solvent is preferably ethanol or acetone; Described water is preferably distilled water.
Complete after the cleaning of described pine needle, the pine needle that the present invention has cleaned is dried, and obtains the pine needle of drying.The present invention does not have special restriction to the method for described oven dry, adopts the technical scheme of oven dry well known to those skilled in the art.In the present invention, the temperature of described oven dry is preferably 50 ℃ ~ 100 ℃.
Complete after the oven dry of described pine needle, the present invention heat-treats the pine needle of having dried under inert atmosphere, obtains the first carbon-based electrode material.In the present invention, described heat treated temperature is preferably 400 ℃ ~ 1500 ℃; More preferably 500 ℃ ~ 1200 ℃; The described heat treated time is preferably 2 hours ~ and 12 hours, more preferably 5 hours ~ 10 hours; Described inert atmosphere is preferably helium atmosphere, argon gas atmosphere or nitrogen atmosphere, more preferably nitrogen atmosphere.
The present invention, after completing the heat treatment of pine needle, is preferably cooled to room temperature by the heat-treated products obtaining, and obtains the first carbon-based electrode material.The raw material of the first carbon-based electrode material obtaining due to the present invention is pine needle, and in the present invention, described the first carbon-based electrode material is also referred to as the first pine needle charcoal.
Obtain after the first carbon-based electrode material, the present invention mixes described the first carbon-based electrode material with alkaline matter, obtain mixture.In order to make described the first carbon-based electrode material surface activation evenly, the present invention preferably mixes described the first carbon-based electrode material and alkaline matter.In the present invention, described alkaline matter is preferably hydroxide, carbonate or bicarbonate, and more preferably one or more in potassium hydroxide, potash, saleratus, NaOH, sodium carbonate, sodium acid carbonate, most preferably are potassium hydroxide; The mass ratio of described alkaline matter and described the first carbon-based electrode material is preferably (1 ~ 16): 1, more preferably (5 ~ 12): 1.
Obtain after the mixture of the first carbon-based electrode material and alkaline matter, the present invention carries out described mixture chemical activation under inert atmosphere, obtains the second carbon-based electrode material.In the process of described chemical activation, described alkaline matter can carry out etching to the surface of described the first carbon-based electrode material, on the surface of described the first carbon-based material, forms deep mixed aperture, obtains the second carbon-based electrode material.In the present invention, described inert atmosphere is preferably helium atmosphere, argon gas atmosphere or nitrogen atmosphere, more preferably nitrogen atmosphere; The temperature of described chemical activation is preferably 800 ℃ ~ 1000 ℃; The time of described chemical activation is preferably 2 hours ~ and 12 hours, more preferably 5 hours ~ 10 hours.
Complete after described chemical activation, the present invention is preferably cooled to room temperature by the chemical activation product obtaining, and then the cooled product obtaining is washed, to remove residual alkali, until washing afterproduct is neutral.The present invention does not have special restriction to the technical scheme of described washing, adopts the technical scheme of washing well known to those skilled in the art.The present invention preferably adopts hot distilled water repeatedly to wash, until washing afterproduct is neutral.
Complete after the washing of described product, the present invention is preferably dried the washed product obtaining, and obtains the second carbon-based electrode material.The present invention be take pine needle and is prepared the second carbon-based electrode material as raw material, and therefore in the present invention, described the second carbon-based electrode material is also referred to as the second pine needle charcoal.The present invention does not have special restriction to the technical scheme of described oven dry, adopts the technical scheme of oven dry well known to those skilled in the art.In the present invention, the temperature of described oven dry is preferably 50 ℃ ~ 100 ℃, more preferably 60 ℃ ~ 80 ℃.
The invention provides a kind of preparation method of carbon-based electrode material, method provided by the invention be take pine needle as raw material, described pine needle can be obtained after Overheating Treatment to the first carbon-based electrode material; After the first carbon-based electrode material obtaining is mixed with alkaline matter, carry out chemical activation and can obtain the second carbon-based electrode material.Method provided by the invention be take pine needle as raw material, and raw material is cheap and easy to get, and raw material is passed through to simple heat treatment or can obtain carbon-based electrode material through Overheating Treatment and chemical activation, therefore, preparation method provided by the invention is simple, and step is easy to control, energy consumption is little, is suitable for large-scale industrial production.And solved the problem of environmental pollution that fallen leaves cause, turn waste into wealth.
The invention provides the carbon-based electrode material that preparation method prepares described in a kind of technique scheme.
Obtain after carbon-based electrode material, the present invention adopts scanning electron microscopy to carry out scanning analysis to the pattern of carbon-based electrode material provided by the invention, result shows, the first carbon-based electrode material surface that the present invention obtains is more smooth, there is pore structure, and along with the raising of heat treatment temperature, the hole result of the first carbon-based electrode material obtaining is more complicated; The surface of the second carbon-based electrode material that the present invention obtains is partly eaten away, and shows the aperture that the depth is different, and along with the raising of heat treatment temperature, this phenomenon is more obvious;
The present invention has measured specific area and the pore-size distribution of the carbon-based electrode material obtaining, and result shows, the specific area of the first carbon-based electrode material provided by the invention is less, and pore-size distribution is wider; The specific area of the second carbon-based electrode material provided by the invention is larger, and pore-size distribution concentrates on micropore level;
The present invention has detected the electric property of the carbon-based electrode material obtaining, and carbon-based electrode material has higher specific discharge capacity, and specific area is little, have extended cycle life, and is suitable for the electrode material as energy storage device.Experimental result shows, the specific discharge capacity of the lithium rechargeable battery that carbon-based electrode material provided by the invention obtains as the positive pole of lithium rechargeable battery is up to 220mAh g
-1, and the capability retention of the lithium ion battery obtaining in 1000 charge and discharge process is higher, illustrates that it has higher cycle life.
The invention provides a kind of energy storage device, its electrode is formed by the carbon-based electrode material described in technique scheme.
In the present invention, described energy storage device can be lithium rechargeable battery, can be also sodium-ion battery, can also be electrochemical capacitor.
In order to make carbon-based electrode material provided by the invention can be used as the electrode of energy storage device, the present invention makes electrode slice by described carbon-based electrode material.The present invention does not have special restriction to the preparation method of described electrode slice, adopts the technical scheme of preparing electrode slice well known to those skilled in the art.In the present invention, described electrode slice preferably obtains in accordance with the following methods:
Described carbon-based electrode material and binding agent and conductive agent are dissolved in organic solvent, obtain slurry;
Described slurry is coated in to post-drying on copper foil of affluxion body;
The product of described oven dry is struck out to disk, obtain electrode slice.
The carbon-based electrode material that the present invention obtains technique scheme and binding agent and conductive agent are dissolved in organic solvent, after mixing, obtain slurry.The present invention preferably first mixes carbon-based electrode material, binding agent and conductive agent, then in the mixture obtaining, drips organic solvent, after mixing, obtains slurry.The present invention does not have special restriction to the kind of described binding agent, conductive agent and organic solvent and consumption, adopts the binding agent for the preparation of electrode slice well known to those skilled in the art, conductive agent and organic solvent.Described binding agent is preferably Kynoar or polytetrafluoroethylene etc. in the present invention; Described conductive agent is preferably acetylene black, conductive carbon black or Ketjen black, more preferably acetylene black or conductive black; Mass ratio between described carbon-based electrode material and described binding agent and conductive agent is preferably (7 ~ 8.5): (1.0 ~ 2): (0.5 ~ 1); Described organic solvent is preferably 1-METHYLPYRROLIDONE or dispersant, and described dispersant is for polymer backbone that can adsorption and have the side chain of non-ionic surface active agent character.
Obtain after slurry, the present invention is coated in post-drying on copper foil of affluxion body by described slurry.The present invention does not have special restriction to thickness of the method for described coating, coating etc., adopts the technical scheme of coating well known to those skilled in the art.The present invention preferably adopts automatic applicator that described slurry is coated on copper foil of affluxion body.The present invention does not have special restriction to the method for described oven dry, adopts the technical scheme of oven dry well known to those skilled in the art.In the present invention, the temperature of described oven dry is preferably 60 ℃ ~ 100 ℃, more preferably 70 ℃ ~ 90 ℃; The time of described oven dry is preferably 8 hours ~ and 20 hours, the time of described oven dry is preferably 10 hours ~ and 15 hours.
Complete after the oven dry of Copper Foil, the present invention strikes out disk by the oven dry product obtaining, and obtains electrode slice.The present invention does not have special restriction to the method for described punching press, adopts the technical scheme of punching press well known to those skilled in the art.The present invention preferably adopts collector stamping machine that the oven dry product obtaining is struck out to disk, and described disk is electrode slice.In the present invention, the diameter of described disk is preferably 1.0cm ~ 2.0cm, more preferably 1.2cm ~ 1.6cm.
When described energy storage device is lithium rechargeable battery, the electrode of described energy storage device is anodal.The present invention does not have special restriction to preparing the method for lithium rechargeable battery, adopts the technical scheme of lithium ion secondary batteries dress well known to those skilled in the art.In the present invention, described lithium rechargeable battery preferably obtains in accordance with the following methods:
The carbon-based electrode material of take described in technique scheme as anodal, lithium metal as negative pole, the organic solution that is dissolved with neutral lithium salts as electrolyte, layer glass fiber be barrier film, assembling obtains lithium rechargeable battery.In the present invention, described neutral lithium salts is preferably LiBF4, lithium hexafluoro phosphate, trifluoromethanesulfonic acid lithium or lithium perchlorate; The solvent of described organic solution is preferably one or both in propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester or GBL, more preferably propene carbonate; The molar concentration of described electrolyte is preferably 1.0mol/L ~ 1.5mol/L; Moisture in described electrolyte is preferably less than 30ppm.
Obtain after lithium rechargeable battery, the present invention adopts LAND series battery test macro to test the performance of the lithium rechargeable battery obtaining, be specially under the operating voltage of 0.005V ~ 2V and the current density of 1mA and carry out charge-discharge test, result shows, the specific discharge capacity of lithium rechargeable battery prepared by carbon-based electrode material provided by the invention is up to 220mAh g
-1; And its capability retention in 1000 charge and discharge process is higher, has higher cycle life.
When described energy storage device is sodium-ion battery, the electrode of described energy storage device is anodal.The present invention does not have special restriction to preparing the method for sodium-ion battery, adopts the technical scheme of sodium-ion battery assembling well known to those skilled in the art.In the present invention, described sodium-ion battery preferably obtains in accordance with the following methods:
The carbon-based electrode material of take described in technique scheme as anodal, sodium metal as negative pole, the organic solution that is dissolved with neutral sodium-salt as electrolyte, layer glass fiber be barrier film, assembling obtains sodium-ion battery.In the present invention, described neutral sodium-salt is preferably sodium tetrafluoroborate, sodium hexafluoro phosphate, trifluoromethanesulfonic acid sodium or sodium perchlorate; The solvent of described organic solution is preferably one or both in propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester or Isosorbide-5-Nitrae-Ding propyl ester, more preferably propene carbonate; The molar concentration of described electrolyte is preferably 1.0mol/L ~ 1.5mol/L; Moisture in described electrolyte is preferably less than 30ppm.
Obtain after sodium-ion battery, the present invention adopts LAND series battery test macro to test the performance of the sodium-ion battery obtaining, be specially under the operating voltage of 0.005V ~ 2V and the current density of 1mA and carry out charge-discharge test, result shows, the specific discharge capacity of sodium-ion battery prepared by carbon-based electrode material provided by the invention is up to 80mAh g
-1; And its capability retention in 1000 charge and discharge process is higher, has higher cycle life.
When described energy storage device is electrochemical capacitor, it can be three-electrode system, can be also two electrode systems.
When described electrochemical capacitor is three-electrode system, the carbon-based electrode material that the technique scheme of take provides is work electrode, take platinum as to electrode, with Ag/AgCl electrode, make reference electrode, the aqueous solution of neutral sodium-salt or neutral lithium salts of take is electrolyte, obtains the electrochemical capacitor of three-electrode system.Described neutral lithium salts and neutral sodium-salt can adopt neutral lithium salts and the neutral sodium-salt described in technique scheme, do not repeat them here; The molar concentration of described electrolyte is preferably 1.0mol/L ~ 1.5mol/L.The present invention preferably makes film by described carbon-based electrode material, usings the film that obtains as work electrode, and the present invention is preferably in accordance with the following methods by described carbon-based electrode material compacting film forming:
After carbon-based electrode material is mixed with electroconductive binder, be coated on collector stainless (steel) wire, and then carry out compressing tablet film forming.In the present invention, the preferred acetylene black of described electroconductive binder and Kynoar, the mass ratio of described carbon-based electrode material and electroconductive binder is preferably (1 ~ 3): 1.
Obtain after electrochemical capacitor, the present invention adopts electrochemical workstation to carry out cyclic voltammetry, and result shows, along with cyclic voltammetry is swept fast increase, cyclic voltammogram curve generation deformation, but also keep general shape, illustrate that the multiplying power property of electrochemical capacitor provided by the invention is better.
When described electrochemical capacitor is two electrode systems, what obtain is symmetric form electrochemical capacitor.Described symmetric form electrochemical capacitor is preparation in accordance with the following methods preferably: the positive pole of described symmetric form electrochemical capacitor and negative pole form by the carbon-based electrode material described in technique scheme, take layer glass fiber as barrier film, the organic solution of quaternary ammonium salt of take is electrolyte, and assembling obtains symmetric form electrochemical capacitor.The present invention does not have special restriction to the assemble method of described symmetric form electrochemical capacitor, adopts the technical scheme to the assembling of moulding electrochemical capacitor well known to those skilled in the art.In the present invention, described quaternary ammonium salt is preferably tetrafluoro boric acid dimethyl diethylamide; The solvent of described organic solution is preferably one or both in propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (EMC), GBL (GBL); The moisture of described electrolyte is preferably less than 30ppm.
Obtain after symmetric form electrochemical capacitor, the present invention adopts LAND series battery test macro to test the performance of the symmetric form electrochemical capacitor obtaining, be specially under the operating voltage of 0V ~ 3.7V and the current density of 1mA and carry out charge-discharge test, result shows, the specific discharge capacity of lithium rechargeable battery prepared by carbon-based electrode material provided by the invention is up to 40mAh g
-1; And its capability retention in 1000 charge and discharge process is higher, has higher cycle life.
The invention provides a kind of carbon-based electrode material, its preparation method and energy storage device.The preparation method of carbon-based electrode material provided by the invention comprises the following steps: a) pine needle is heat-treated under inert atmosphere, obtain the first carbon-based electrode material; B) the first carbon-based electrode material described step a) being obtained mixes with alkaline matter, obtains mixture; C) mixture described step b) being obtained carries out chemical activation under inert atmosphere, obtains the second carbon-based electrode material.Preparation method provided by the invention be take pine needle as raw material, and abundant raw material can obtain the first carbon-based electrode material by pine needle through Overheating Treatment; After the first carbon-based material obtaining is mixed with alkaline matter, carry out chemical activation, can obtain the second carbon-based electrode material.Method step provided by the invention is simple, and operating process is easy to control, and energy consumption is little, is suitable for industrial needs; And raw material is cheap and easy to get, thereby make preparation method provided by the invention there is lower cost.And the carbon-based electrode material that preparation method of the present invention obtains has higher ratio electric capacity, specific area is little, have extended cycle life, can be as the electrode of energy storage device.Experimental result shows, carbon-based electrode material provided by the invention, when as lithium ion secondary battery positive electrode, sodium-ion battery positive pole and electrochemical capacitor electrode, has higher specific capacity and cycle performance preferably.
In order to further illustrate the present invention, below in conjunction with embodiment, carbon-based electrode material provided by the invention, its preparation method and the application in energy storage device thereof are elaborated, but they can not be interpreted as to limiting the scope of the present invention.
In the following embodiments, scanning electron microscopy is that the model that PHILIPS Co. produces is XL-30ESEM type, and accelerating voltage is 15kV in use; Full-automatic specific area and porous analyzer are that the model that Micromeritics Instrument Corp. U.S.A produces is ASAP 2020 types; The model of electrochemical workstation is CHI660C.
Ultrasonic 10min after pine needle water is cleaned, then cleans with ethanol or acetone, more ultrasonic 10min, finally with distilled water, cleans, by the clean pine needle obtaining dry for standby at 70 ℃.
The pine needle of getting above-mentioned oven dry heat treated 2 hours under nitrogen atmosphere protection, described heating-up temperature is 500 ℃, obtains the first carbon-based electrode material.
The present invention adopts scanning electron microscopy to characterize the pattern of the first carbon-based electrode material obtaining, result as shown in Figure 1, Fig. 1 is the SEM figure of the first carbon-based electrode material of obtaining of the embodiment of the present invention 1, as seen from Figure 1, the first carbon-based electrode material that the present embodiment obtains has pore structure.
The first carbon-based electrode material specific area and pore-size distribution that the present invention adopts full-automatic specific area and porous analyzer to characterize to obtain, as shown in Figure 2, Fig. 2 is BJH graph of pore diameter distribution and the N of the first carbon-based electrode material of obtaining of the embodiment of the present invention 1 to result
2adsorption-desorption isothermal linearity curve, wherein curve a is the BJH graph of pore diameter distribution of the first carbon-based electrode material of obtaining of the embodiment of the present invention 1, curve b is the N of the first carbon-based electrode material of obtaining of the embodiment of the present invention 1
2adsorption-desorption isothermal linearity curve, the specific area that obtains the first carbon-based electrode material of this enforcement preparation according to the curve calculation of Fig. 2 a is 11.639m
2/ g, can be found out by Fig. 2 b, and the pore-size distribution of the first carbon-based electrode material prepared by the present embodiment is compared with wide and adsorbance is few.
The pine needle of the oven dry that embodiment 1 is obtained heat treated 3 hours under nitrogen atmosphere protection, described heating-up temperature is 600 ℃, obtains the first carbon-based electrode material.
The present invention adopts scanning electron microscopy to characterize the pattern of the first carbon-based electrode material obtaining, result as shown in Figure 3, Fig. 3 is the SEM figure of the first carbon-based electrode material of obtaining of the embodiment of the present invention 2, as seen from Figure 3, the first carbon-based electrode material that the present embodiment obtains has pore structure.
The first carbon-based electrode material specific area and pore-size distribution that the present invention adopts full-automatic specific area and porous analyzer to characterize to obtain, as shown in Figure 4, Fig. 4 is BJH graph of pore diameter distribution and the N of the first carbon-based electrode material of obtaining of the embodiment of the present invention 2 to result
2adsorption-desorption isothermal linearity curve, wherein curve a is the BJH graph of pore diameter distribution of the first carbon-based electrode material of obtaining of the embodiment of the present invention 2, curve b is the N of the first carbon-based electrode material of obtaining of the embodiment of the present invention 2
2adsorption-desorption isothermal linearity curve, the specific area that obtains the first carbon-based electrode material prepared by the present embodiment according to Fig. 4 a curve calculation is 113.635m
2/ g, can be found out by Fig. 4 b, and the pore-size distribution of the first carbon-based electrode material prepared by the present embodiment is compared with wide and adsorbance is few.
The pine needle of the oven dry that embodiment 1 is obtained heat treated 4 hours under nitrogen atmosphere protection, described heating-up temperature is 700 ℃, obtains the first carbon-based electrode material.
The present invention adopts scanning electron microscopy to characterize the pattern of the first carbon-based electrode material obtaining, result as shown in Figure 5, Fig. 5 is the SEM figure of the first carbon-based electrode material of obtaining of the embodiment of the present invention 3, as seen from Figure 5, the first carbon-based electrode material that prepared by the present embodiment has pore structure.
The first carbon-based electrode material specific area and pore-size distribution that the present invention adopts full-automatic specific area and porous analyzer to characterize to obtain, result shows, the pore-size distribution of the first carbon-based electrode material prepared by the present embodiment is compared with wide and adsorbance is few.
The pine needle of the oven dry that embodiment 1 is obtained heat treated 6 hours under nitrogen atmosphere protection, described heating-up temperature is 800 ℃, obtains the first carbon-based electrode material.
The present invention mixes the first carbon-based electrode material obtaining with alkaline matter, then, by the mixture obtaining chemical activation 10 hours under nitrogen atmosphere protection, activation temperature is 800 ℃.After completing chemical activation, the product obtaining is cooled to room temperature, the distilled water of reusable heat washs to remove residual alkaline matter, until pH value is neutral.By pH value, be finally that neutral product is dried at 70 ℃, obtain the second carbon-based electrode material.
The present invention adopts scanning electron microscopy to characterize the first carbon-based electrode material obtaining and the pattern of the second carbon-based electrode material, result as shown in Figure 6 and Figure 7, Fig. 6 is the SEM figure of the first carbon-based electrode material of obtaining of the embodiment of the present invention 4, as seen from Figure 6, the first carbon-based electrode material that the present embodiment obtains has pore structure; Fig. 7 is the SEM figure of the second carbon-based electrode material of obtaining of the embodiment of the present invention 4, and as seen from Figure 7, the second carbon-based electrode surface that the present embodiment obtains has deep mixed aperture.
The first carbon-based electrode material that the present invention adopts full-automatic specific area and porous analyzer to characterize to obtain and specific area and the pore-size distribution of the second carbon-based electrode material, as shown in Figure 8 and Figure 9, Fig. 8 is BJH graph of pore diameter distribution and the N of the first carbon-based electrode material of obtaining of the embodiment of the present invention 4 to result
2adsorption-desorption isothermal linearity curve, wherein curve a is the BJH graph of pore diameter distribution of the first carbon-based electrode material of obtaining of the embodiment of the present invention 4, curve b is the N of the first carbon-based electrode material of obtaining of the embodiment of the present invention 4
2adsorption-desorption isothermal linearity curve, the specific area that obtains the first carbon-based electrode material prepared by the present embodiment according to Fig. 8 a curve calculation is 2.182m
2/ g, can be found out by Fig. 8 b, and the pore-size distribution of the first carbon-based electrode material prepared by the present embodiment is compared with wide and adsorbance is few;
Fig. 9 is BJH graph of pore diameter distribution and the N of the second carbon-based electrode material of obtaining of the embodiment of the present invention 4
2adsorption-desorption isothermal linearity curve, wherein curve a is the BJH graph of pore diameter distribution of the second carbon-based electrode material of obtaining of the embodiment of the present invention 4, curve b is the N of the second carbon-based electrode material of obtaining of the embodiment of the present invention 4
2adsorption-desorption isothermal linearity curve, the specific area that obtains the second carbon-based electrode material prepared by the present embodiment according to Fig. 9 a curve calculation is 1111.8207m
2/ g, can be found out by Fig. 9 b, and the pore-size distribution of the second carbon-based electrode material prepared by the present embodiment concentrates on micropore, and adsorbance is larger.
Embodiment 5
The pine needle of the oven dry that embodiment 1 is obtained heat treated 8 hours under nitrogen atmosphere protection, described heating-up temperature is 900 ℃, obtains the first carbon-based electrode material.
The present invention adopts scanning electron microscopy to characterize the pattern of the first carbon-based electrode material obtaining, result as shown in figure 10, Figure 10 is the SEM figure of the first carbon-based electrode material of obtaining of the embodiment of the present invention 5, as seen from Figure 10, the first carbon-based electrode material prepared by the embodiment of the present invention has pore structure, and pore structure is more complicated.
The first carbon-based electrode material specific area and pore-size distribution that the present invention adopts full-automatic specific area and porous analyzer to characterize to obtain, result shows, the pore-size distribution of the first carbon-based electrode material prepared by the present embodiment is compared with wide and adsorbance is few.
The pine needle of the oven dry that embodiment 1 is obtained heat treated 10 hours under nitrogen atmosphere protection, described heating-up temperature is 1000 ℃, obtains the first carbon-based electrode material.
The present invention mixes the first carbon-based electrode material obtaining with alkaline matter, then, by the mixture obtaining chemical activation 5 hours under nitrogen atmosphere protection, activation temperature is 800 ℃.After completing chemical activation, the product obtaining is cooled to room temperature, the distilled water of reusable heat washs to remove residual alkaline matter, until pH value is neutral.By pH value, be finally that neutral product is dried at 70 ℃, obtain the second carbon-based electrode material.
The present invention adopts scanning electron microscopy to characterize the first carbon-based electrode material obtaining and the pattern of the second carbon-based electrode material, result is as shown in Figure 11 and Figure 12, Figure 11 is the SEM figure of the first carbon-based electrode material of obtaining of the embodiment of the present invention 6, as seen from Figure 11, the first carbon-based electrode material that prepared by the present embodiment has complicated pore structure; Figure 12 is the SEM figure of the second carbon-based electrode material of obtaining of the embodiment of the present invention 6, and as seen from Figure 12, the second carbon-based electrode material surface prepared by the present embodiment has deep mixed aperture.
The first carbon-based electrode material that the present invention adopts full-automatic specific area and porous analyzer to characterize to obtain and specific area and the pore-size distribution of the second carbon-based electrode material, as shown in Figure 13 and Figure 14, Figure 13 is BJH graph of pore diameter distribution and the N of the first carbon-based electrode material of obtaining of the embodiment of the present invention 6 to result
2adsorption-desorption isothermal linearity curve, wherein curve a is the BJH graph of pore diameter distribution of the first carbon-based electrode material of obtaining of the embodiment of the present invention 6, curve b is the N of the first carbon-based electrode material of obtaining of the embodiment of the present invention 6
2adsorption-desorption isothermal linearity curve, the specific area that obtains the first carbon-based electrode material prepared by the present embodiment according to Figure 13 a curve calculation is 0.4149m
2/ g; By Figure 13 b, can be found out, the pore-size distribution of the first carbon-based electrode material prepared by the present embodiment is compared with wide and adsorbance is few;
Figure 14 is BJH graph of pore diameter distribution and the N of the second carbon-based electrode material of obtaining of the embodiment of the present invention 6
2adsorption-desorption isothermal linearity curve, wherein curve a is the BJH graph of pore diameter distribution of the second carbon-based electrode material of obtaining of the embodiment of the present invention 6, curve b is the N of the second carbon-based electrode material of obtaining of the embodiment of the present invention 6
2adsorption-desorption isothermal linearity curve, the specific area that obtains the second carbon-based electrode material prepared by the present embodiment according to Figure 14 a curve calculation is 1095.1134m
2/ g; By Figure 14 b, can be found out, the pore-size distribution of the second carbon-based electrode material prepared by the present embodiment concentrates on micropore, and has higher adsorbance.
Embodiment 7 ~ 12
The the first carbon-based electrode material respectively embodiment 1 ~ 6 being obtained with Kynoar, acetylene black in mass ratio for the ratio of 8:1:1 is mixed, drip 1-METHYLPYRROLIDONE by mixture furnishing slurry, use automatic spray device that slurry is evenly coated on copper foil of affluxion body, then under 80 ° of C, dry 12 hours, finally with collector stamping machine, being struck out diameter is that the electrode wafer of 1.4cm is standby.
After electrode slice and barrier film are dried to 6 hours under 110 ℃ of vacuum states, move in the glove box that anhydrous and oxygen-free is full of argon gas and assemble capacitor.The electrode wafer of preparing with the present embodiment is done anodal, and lithium metal is made negative pole, and layer glass fiber is barrier film, and the organic solution of the lithium hexafluoro phosphate that molar concentration is 1.0mol/L is that electrolyte (moisture is less than 30ppm) is assembled into button cell.
The present invention connects LAND series battery test macro, and the button cell under the operating voltage of 0.005V ~ 2V and 1mA current density, the present embodiment being obtained carries out charge-discharge test.Result as shown in figure 15, Figure 15 is the specific capacity curve chart of the lithium ion battery that obtains of the embodiment of the present invention 7 ~ 12, the specific capacity curve of the lithium ion battery that wherein curve 1 obtains for embodiment 7, the specific capacity curve of the lithium ion battery that curve 2 obtains for embodiment 8, the specific capacity curve of the lithium ion battery that curve 3 obtains for embodiment 9, the specific capacity curve of the lithium ion battery that curve 4 obtains for embodiment 10, the specific capacity curve of the lithium ion battery that curve 5 obtains for embodiment 11, the specific capacity curve of the lithium ion battery that curve 6 obtains for embodiment 12, as seen from Figure 15, the specific discharge capacity of doing the lithium ion battery that positive pole obtains with carbon-based electrode material provided by the invention can reach 220mAh g
-1.
Embodiment 13
The the first carbon-based electrode material obtaining with embodiment 5 is done anodal, and lithium metal is made negative pole, and the organic solution of the lithium hexafluoro phosphate that molar concentration is 1.0mol/L is electrolyte, and layer glass fiber is barrier film, is assembled into button cell.
The present invention connects the chemical property of the button cell that LAND series battery test macro obtains the present embodiment and tests, under the operating voltage of 0.005V ~ 2V and 1mA current density, discharge and recharge 1000 times, result as shown in figure 16, Figure 16 is the cycle charge-discharge curve of the lithium ion battery that obtains of the embodiment of the present invention 13, in Figure 16, solid black point represents electric discharge, and grey solid dot represents charging.As seen from Figure 16, solid black point and grey solid dot overlap substantially, this explanation, and the capability retention of lithium ion battery in 1000 charge and discharge process is higher, illustrates that cycle life is better.
Embodiment 14 ~ 19
The the first carbon-based electrode material obtaining with embodiment 1 ~ 6 is respectively done anodal, sodium metal is made negative pole, layer glass fiber is barrier film, and the organic solution of the sodium hexafluoro phosphate that molar concentration is 1.0mol/L is that electrolyte (moisture is less than 30ppm) is assembled into button cell.
The chemical property of the button cell that connection LAND series battery test macro obtains embodiment 14 ~ 19 is tested, under the operating voltage of 0.005V ~ 2V and 1mA current density, carry out charge-discharge test, result as shown in figure 17, Figure 17 is the specific capacity curve chart of the sodium-ion battery that obtains of the embodiment of the present invention 14 ~ 19, the specific capacity curve of the sodium-ion battery that wherein curve 1 obtains for the embodiment of the present invention 14, the specific capacity curve of the sodium-ion battery that curve 2 obtains for the embodiment of the present invention 15, the specific capacity curve that curve 3 is the sodium-ion battery that uses the embodiment of the present invention 16 and obtain, the specific capacity curve of the sodium-ion battery that curve 4 obtains for the embodiment of the present invention 17, the specific capacity curve of the sodium-ion battery that curve 5 obtains for the embodiment of the present invention 18, the specific capacity curve of the sodium-ion battery that curve 6 obtains for the embodiment of the present invention 19, as seen from Figure 17, the specific discharge capacity of doing the sodium-ion battery that positive pole obtains with carbon-based electrode material provided by the invention can reach nearly 80mAh g
-1.
With embodiment 5, obtain the first carbon-based electrode material and make positive pole, sodium metal is made negative pole, and the organic solution of the sodium hexafluoro phosphate that molar concentration is 1.0mol/L is electrolyte (moisture is less than 30ppm), and layer glass fiber is barrier film, is assembled into button cell.
The present invention connects the chemical property of the button cell that LAND series battery test macro obtains the present embodiment and tests, under the operating voltage of 0.005V ~ 2V and 1mA current density, discharge and recharge 1000 times, result as shown in figure 18, Figure 18 is the cycle charge-discharge curve of the sodium-ion battery that obtains of embodiment 20, in Figure 18, solid black point represents electric discharge, and grey solid dot represents charging.As seen from Figure 18, solid black point and grey solid dot overlap substantially, this explanation, and the capability retention of sodium-ion battery in 1000 charge and discharge process is higher, illustrates that cycle life is better.
Embodiment 21
The first carbon-based electrode material that 10mg embodiment 4 is obtained and 5mg acetylene black, Kynoar mix and are coated in compressing tablet film forming on collector stainless (steel) wire, the the first carbon-based electrode material obtaining with embodiment 4 is made work electrode, platinum is done electrode, Ag/AgCl electrode is made reference electrode, molar concentration is that the sodium perchlorate aqueous solution of 1.0mol/L is electrolyte, is assembled into three-electrode system.
Connect electrochemical workstation CHI660C, under the operating voltage of 0.5V ~-0.7V, adopt three-electrode system to carry out cyclic voltammetry, result as shown in figure 19, Figure 19 is that the three-electrode system that embodiment 21 obtains is swept the cyclic voltammogram under speed in difference, wherein curve a is the cyclic voltammetry curve of sweeping under fast 5mV/s, curve b is the cyclic voltammetry curve of sweeping under fast 10mV/s, curve c is the cyclic voltammetry curve of sweeping under fast 20mV/s, curve d is the cyclic voltammetry curve of sweeping under fast 50mV/s, curve e is the cyclic voltammetry curve of sweeping under fast 100mV/s, curve f is the cyclic voltammetry curve of sweeping under fast 150mV/s, curve g is the cyclic voltammetry curve of sweeping under fast 200mV/s, as seen from Figure 19, along with sweeping fast increase, cyclic voltammogram curve generation deformation, but also keep general shape, illustrate that its multiplying power property is better.
Embodiment 22 ~ 27
The the first carbon-based electrode material respectively 10mg embodiment 2 ~ 3 being obtained, the first carbon-based electrode material that embodiment 4 and embodiment 6 obtain and the second carbon-based electrode material and 5mg acetylene black, Kynoar mixes and is coated in compressing tablet film forming on collector stainless (steel) wire, the the first carbon-based electrode material obtaining with embodiment 2 ~ 3 respectively, the first carbon-based electrode material and the second carbon-based electrode material that embodiment 4 and embodiment 6 obtain are made work electrode, platinum is done electrode, Ag/AgCl electrode is made reference electrode, molar concentration is that the sodium perchlorate aqueous solution of 1.0mol/L is electrolyte, be assembled into three-electrode system.
Connect electrochemical workstation CHI660C, under the operating voltage of 0.5V ~ 0.7V, sweeping fast 5mV/s respectively, 10mV/s, 20mV/s, 50mV/s, 100mV/s, 150mV/s, under 200mV/s, carry out cyclic voltammetry, result as shown in figure 20, Figure 20 be the capacitor that obtains of the embodiment of the present invention 22 ~ 27 sweep speed-than capacitance relation figure, the ratio electric capacity of the capacitor that wherein curve 1 obtains for embodiment 22, the ratio electric capacity of the capacitor that curve 2 obtains for embodiment 23, the ratio electric capacity of the capacitor that curve 3 obtains for embodiment 24, the ratio electric capacity of the capacitor that curve 4 obtains for embodiment 25, the ratio electric capacity of the capacitor that curve 5 obtains for embodiment 26, the ratio electric capacity of the capacitor that curve 6 obtains for embodiment 27.As seen from Figure 20, the ratio electric capacity of the capacitor that embodiment 22 ~ 25 obtains is less, and along with sweeping fast increase, the amplitude more less than electric capacity is less, and this explanation has good multiplying power property; The capacitor that embodiment 26 ~ 27 obtains has higher ratio electric capacity while sweeping speed low, but along with sweeping fast increase, than electric capacity, reduce, particularly sweep speed when the 50mV/s than the rapid decline of electric capacity, tend to be steady afterwards, the multiplying power property variation of the second carbon-based electrode material obtaining after visible activation.
Embodiment 28 ~ 29
The second carbon-based electrode material that embodiment 4 is obtained is made positive pole and negative pole, the second carbon-based electrode material that embodiment 6 is obtained is made positive pole and negative pole, layer glass fiber is barrier film, and the organic solution of the tetrafluoro boric acid dimethyl diethylamide that molar concentration is 1mol/L is that electrolyte (moisture is less than 30ppm) is assembled into symmetric form electrochemical capacitor.
Connect LAND series battery test macro, the electrochemical capacitor under the operating voltage of 0V ~ 3.7V and 0.1mA current density, the present embodiment being obtained carries out charge-discharge test, result as shown in figure 21, Figure 21 is the specific capacity curve chart of the symmetric form electrochemical capacitor that obtains of the embodiment of the present invention 28 ~ 29, the specific capacity curve of the symmetric form electrochemical capacitor that in figure, curve 1 obtains for the embodiment of the present invention 28, the specific capacity curve of the symmetric form electrochemical capacitor that curve 2 obtains for the embodiment of the present invention 29.The discharge capacity of the symmetry electrochemical capacitor that as seen from Figure 21, the second carbon-based electrode material provided by the invention obtains can reach 40mAh g
-1, illustrate that the second carbon-based electrode material that pine needle charcoal obtains after activated can be used as the electrode material of the electrochemical capacitor of organic system.
As seen from the above embodiment, the invention provides a kind of carbon-based electrode material, its preparation method and energy storage device.Preparation method provided by the invention be take pine needle as raw material, and abundant raw material can obtain the first carbon-based electrode material by pine needle through Overheating Treatment; After the first carbon-based material obtaining is mixed with alkaline matter, carry out chemical activation, can obtain the second carbon-based electrode material.Method step provided by the invention is simple, and operating process is easy to control, and energy consumption is little, is suitable for industrial needs; And raw material is cheap and easy to get, thereby make preparation method provided by the invention there is lower cost.And the carbon-based electrode material that preparation method of the present invention obtains has higher ratio electric capacity, specific area is little, have extended cycle life, can be as the electrode of energy storage device.Experimental result shows, carbon-based electrode material provided by the invention, when as lithium ion secondary battery positive electrode, sodium-ion battery positive pole and electrochemical capacitor electrode, has higher specific capacity and cycle performance preferably.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a preparation method for carbon-based electrode material, comprises the following steps:
A) pine needle is heat-treated under inert atmosphere, obtain the first carbon-based electrode material;
B) the first carbon-based electrode material described step a) being obtained mixes with alkaline matter, obtains mixture;
C) mixture described step b) being obtained carries out chemical activation under inert atmosphere, obtains the second carbon-based electrode material.
2. preparation method according to claim 1, is characterized in that, the heat treatment temperature of described step a) is 400 ℃ ~ 1500 ℃;
The heat treatment time of described step a) is 2 hours ~ 12 hours.
3. preparation method according to claim 1, is characterized in that, the alkaline matter in described step b) is hydroxide, carbonate or bicarbonate.
4. preparation method according to claim 1, is characterized in that, the mass ratio of described step b) neutral and alkali material and the first carbon-based electrode material is (1 ~ 16): 1.
5. preparation method according to claim 1, is characterized in that, the temperature of the chemical activation of described step b) is 800 ℃ ~ 1000 ℃;
The time of the chemical activation of described step c) is 2 hours ~ 12 hours.
6. the carbon-based electrode material being obtained by preparation method described in claim 1 ~ 5 any one.
7. an energy storage device, is characterized in that, electrode is formed by carbon-based electrode material claimed in claim 6.
8. energy storage device according to claim 7, is characterized in that, described energy storage device is lithium rechargeable battery, and described electrode is anodal.
9. energy storage device according to claim 7, is characterized in that, described energy storage device is sodium-ion battery, and described electrode is anodal.
10. energy storage device according to claim 7, is characterized in that, described energy storage device is electrochemical capacitor.
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| CN105406125A (en) * | 2014-09-11 | 2016-03-16 | 中国科学院长春应用化学研究所 | Dual-ion battery |
| CN105719840A (en) * | 2016-01-25 | 2016-06-29 | 新余学院 | Preparation method of leafy biomass pyrolytic carbon counter electrode for dye-sensitized solar cell |
| CN105858636A (en) * | 2016-04-05 | 2016-08-17 | 陕西科技大学 | Method for preparing pine needle derived micro-nano structure hard carbon material |
| CN107555430A (en) * | 2017-09-01 | 2018-01-09 | 中国林业科学研究院林产化学工业研究所 | A kind of ultracapacitor pine needle matrix activated carbon and one step charing preparation method |
| CN107651685A (en) * | 2017-10-27 | 2018-02-02 | 江苏大学 | A kind of method that chemical activation prepares multiporous biological matter charcoal |
| CN108365184A (en) * | 2018-01-02 | 2018-08-03 | 江苏大学 | A kind of lithium ion battery porous SiOC negative materials of rich carbon and preparation method thereof |
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| CN105406125A (en) * | 2014-09-11 | 2016-03-16 | 中国科学院长春应用化学研究所 | Dual-ion battery |
| CN105719840A (en) * | 2016-01-25 | 2016-06-29 | 新余学院 | Preparation method of leafy biomass pyrolytic carbon counter electrode for dye-sensitized solar cell |
| CN105858636A (en) * | 2016-04-05 | 2016-08-17 | 陕西科技大学 | Method for preparing pine needle derived micro-nano structure hard carbon material |
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| CN107651685A (en) * | 2017-10-27 | 2018-02-02 | 江苏大学 | A kind of method that chemical activation prepares multiporous biological matter charcoal |
| CN108365184A (en) * | 2018-01-02 | 2018-08-03 | 江苏大学 | A kind of lithium ion battery porous SiOC negative materials of rich carbon and preparation method thereof |
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Application publication date: 20140326 |