CN108033447A - Preparation method, multiporous biological matter carbon and the application of multiporous biological matter carbon - Google Patents

Preparation method, multiporous biological matter carbon and the application of multiporous biological matter carbon Download PDF

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Publication number
CN108033447A
CN108033447A CN201711285423.2A CN201711285423A CN108033447A CN 108033447 A CN108033447 A CN 108033447A CN 201711285423 A CN201711285423 A CN 201711285423A CN 108033447 A CN108033447 A CN 108033447A
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small
biological matter
multiporous biological
matter carbon
preparation
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CN108033447B (en
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李义
李纯
于开锋
曹兴刚
王中书
邹康迪
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NALON BATTERY (SHEN ZHEN) CO Ltd
Jilin University
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NALON BATTERY (SHEN ZHEN) CO Ltd
Jilin University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention relates to a kind of preparation method of multiporous biological matter carbon, multiporous biological matter carbon and application.A kind of preparation method of multiporous biological matter carbon, comprises the following steps:Stood after stalk is mixed with calcium chloride solution 12 it is small when~24 it is small when obtain mixture, wherein the mass ratio of the calcium chloride in the stalk and the calcium chloride solution is 1:1.5~1:3;By the mixture be dried processing after at 300 DEG C~350 DEG C low-temperature carbonization processing 2 it is small when~3 it is small when obtain cryogenic carbon compound;By the cryogenic carbon compound be heated to 500 DEG C~700 DEG C carry out high-temperature activations processing 1 it is small when~3 it is small when obtain pre-product;And by the pre-product using inorganic acid immersion 12 it is small when~24 it is small when, then with 70 DEG C~80 DEG C of water washing to neutrality obtain multiporous biological matter carbon.Multiporous biological matter carbon prepared by the preparation method of above-mentioned multiporous biological matter carbon can improve lithium ion battery charging and discharging capacity and cyclical stability.

Description

Preparation method, multiporous biological matter carbon and the application of multiporous biological matter carbon
Technical field
The present invention relates to a kind of preparation method of multiporous biological matter carbon, multiporous biological matter carbon and application.
Background technology
With social economy rapid development and population increase, people are increasing for energy demand, yet with oil, The fossil energies such as coal, natural gas it is non-renewable, and cannot gradually meet that economy and society is sent out after prolonged exploitation The needs of exhibition.In addition, a large amount of greenhouse gases and toxic gas that are produced after fossil energy burning, are also endangering our existence ring Border.In recent years, with the improvement of people's environmental awareness, people are higher and higher for the cry of clean energy resource, exploitation cleaning, height Effect, energy saving new energy, which substitute fossil energy, becomes the hot spot that researchers pay close attention to.
Lithium ion is just received significant attention as a kind of cleaning, efficient green power supply, since the advent of the world, compared to tradition Battery, lithium ion battery has the advantages that operating voltage is high, operating temperature range is wide, energy density is big, memory-less effect. In recent years, as the popularization of intelligent electronic device, lithium ion battery are obtained in mobile phone, digital camera, intelligent watch etc. To extensive use.In addition, the application for fields such as electric car, new-energy automobile, aerospace and military equipments both at home and abroad Also expand and energetically study and apply.Therefore, lithium ion battery becomes a current big research tendency, improves battery specific volume Amount, circulating ratio and cyclical stability become the principal concern of Study on Li-ion batteries.
Negative material is one of critical material of lithium ion battery, and carbon material is as the earliest lithium battery studied and apply Negative material still receives significant attention so far.Crop material is burned as agricultural wastes holds fire hazardous, while discharges big Carbon dioxide aggravation carbon dioxide effect is measured, therefore activated carbon is obtained to stalk progress carbonization treatment and obtains certain research.So And the activated carbon that existing preparation method obtains as lithium ion battery negative material when, the charge/discharge capacity of lithium ion battery It is poor with cyclical stability.
The content of the invention
Based on this, it is necessary to provide a kind of porous life that can improve lithium ion battery charging and discharging capacity and cyclical stability Preparation method, multiporous biological matter carbon and the application of material carbon.
A kind of preparation method of multiporous biological matter carbon, comprises the following steps:
After stalk is mixed with calcium chloride solution stand 12 it is small when~24 it is small when obtain mixture, wherein the stalk and institute The mass ratio for stating the calcium chloride in calcium chloride solution is 1:1.5~1:3;
By the mixture be dried processing after at 300 DEG C~350 DEG C low-temperature carbonization processing 2 it is small when~3 it is small when obtain To cryogenic carbon compound;
By the cryogenic carbon compound be heated to 500 DEG C~700 DEG C carry out high-temperature activations processing 1 it is small when~3 it is small when obtain it is pre- Product;And
By the pre-product using inorganic acid immersion 12 it is small when~24 it is small when, then with 70 DEG C~80 DEG C of water washing into Property obtains multiporous biological matter carbon.
The preparation method of above-mentioned multiporous biological matter carbon, has the following advantages:
(1), it is cheap and easy to get using stalk as carbon source, resource reutilization is realized, reduces environmental pollution;
(2), using can be cheap using the calcium chloride of circulation and stress as activator, production cost be reduced;
(3), the multiporous biological matter carbon of preparation can be easily controlled by the concentration and dosage that adjust calcium chloride solution Pore size;
(4), calcium chloride has good flame retardant effect, in straw-carbonized and activated process, can effectively prevent red-hot The oxidation of charcoal, can improve the yield of activated carbon;
(5), negative material of the multiporous biological matter carbon prepared as lithium ion battery, can improve the electric discharge of lithium ion battery Specific capacity and cyclical stability.
In one of the embodiments, the stalk is maize straw;And/or
The stalk is powdered.
In one of the embodiments, the inorganic acid is selected from least one of hydrochloric acid, sulfuric acid and nitric acid.
In one of the embodiments, the concentration of the inorganic acid is 2mol/L~6mol/L.
In one of the embodiments, the pre-product and the inorganic acid solid-to-liquid ratio are 1g:10mL~1g:20mL.
In one of the embodiments, it is described that the low temperature at 300 DEG C~350 DEG C is dried after processing in the mixture When carbonization treatment 2 is small~3 it is small when the step of obtaining cryogenic carbon compound in, the mixture is dried to progress at 60 DEG C~70 DEG C Drying process.
In one of the embodiments, it is described by the pre-product using inorganic acid immersion 12 it is small when~24 it is small when Before step, step is further included:Using pre-product described in water washing, calcium chloride solution is recycled.
In one of the embodiments, step is further included:Ground after the multiporous biological matter carbon is dried.
The multiporous biological matter carbon that the preparation method of above-mentioned multiporous biological matter carbon obtains.
The application of above-mentioned multiporous biological matter carbon in the battery.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph that multiporous biological matter carbon prepared by embodiment 1 amplifies 80000 times;
Fig. 2 is the transmission electron microscope photo that multiporous biological matter carbon prepared by embodiment 1 amplifies 30000 times;
Fig. 3 is the discharge curve under the current density using the lithium ion battery 0.2C of the multiporous biological matter carbon of embodiment 1 Figure;
Fig. 4 is the charging curve under the current density using the lithium ion battery 0.2C of the multiporous biological matter carbon of embodiment 1 Figure;
Fig. 5 is the discharge curve under the current density using the lithium ion battery 0.2C of the multiporous biological matter carbon of comparative example 1 Figure;
Fig. 6 is the charging curve under the current density using the lithium ion battery 0.2C of the multiporous biological matter carbon of comparative example 1 Figure;
Fig. 7 is the discharge curve under the current density using the lithium ion battery 0.2C of the multiporous biological matter carbon of comparative example 2 Figure;
Fig. 8 is the charging curve under the current density using the lithium ion battery 0.2C of the multiporous biological matter carbon of comparative example 2 Figure.
Embodiment
The preparation method of multiporous biological matter carbon, multiporous biological matter carbon and application are carried out below in conjunction with embodiment Further describe in detail.
The preparation method of the multiporous biological matter carbon of one embodiment, comprises the following steps:
Step S110, after stalk is mixed with calcium chloride solution stand 12 it is small when~24 it is small when obtain mixture, wherein straw The mass ratio of stalk and the calcium chloride in calcium chloride solution is 1:1.5~1:3.
In one of the embodiments, stalk is maize straw.Certainly, in other embodiments, stalk can also be small The remainder of wheat, rice, potato, rape, cotton, sugarcane or other coarse food grain crops after seed is harvested.
In one of the embodiments, stalk is crushed, the stalk after crushing is mixed with calcium chloride solution.
In one of the embodiments, stalk is powdered.Preferably, the particle diameter of stalk powder is micro- for 800 microns~900 Rice, is preferably 850 microns.
In one of the embodiments, the concentration of calcium chloride solution is 2mol/L~4mol/L, is preferably 3mol/L.
In one of the embodiments, the solid-to-liquid ratio of stalk and calcium chloride solution is 10g:200mL~30g:200mL, it is excellent Elect 20g as:200mL.
In one of the embodiments, stood at room temperature after stalk is mixed with calcium chloride solution 12 it is small when~24 it is small when Mixture is obtained, when preferably standing 24 is small.
In one of the embodiments, the mass ratio of stalk and the calcium chloride in calcium chloride solution is 1:2.5.
When mixture step S120, being dried after processing low-temperature carbonization processing 2 is small at 300 DEG C~350 DEG C~3 small When obtain cryogenic carbon compound.
In one of the embodiments, mixture is dried at 60 DEG C~70 DEG C and processing is dried.Preferably, 60 Constant temperature drying at DEG C.
In one of the embodiments, mixture is placed in baking oven and processing is dried.
In one of the embodiments, with the heating rate of 8 DEG C/min~10 DEG C/min by stalk be heated to 300 DEG C~ 350 DEG C of progress carbonization treatments.
In one of the embodiments, the low-temperature carbonization processing at 300 DEG C is dried after processing in mixture.
In one of the embodiments, mixture is dried processing to be placed in crucible with cover, in Muffle furnace into The processing of row low-temperature carbonization.
In one of the embodiments, when the time of low-temperature carbonization processing is 2 small.
Step S130, by cryogenic carbon compound be heated to 500 DEG C~700 DEG C carry out high-temperature activations processing 1 it is small when~3 it is small when obtain To pre-product.
In one of the embodiments, cryogenic carbon compound is heated to 600 DEG C of progress high-temperature activation processing.
In one of the embodiments, when the time of high-temperature activation processing is 2 small.
In one of the embodiments, cryogenic carbon compound is placed in crucible with cover, high-temperature activation is carried out in Muffle furnace Processing.
In one of the embodiments, cryogenic carbon compound is heated to 500 with the heating rate of 8 DEG C/min~10 DEG C/min DEG C~700 DEG C of progress carbonization treatments.
In one of the embodiments, cryogenic carbon compound is heated to 500 DEG C~700 DEG C to carry out high-temperature activations processing 1 small When~3 it is small when, cooled to room temperature obtains pre-product.
In one of the embodiments, using water washing pre-product, it is recycled calcium chloride solution.Preferably, using going Ionized water is washed, and the ratio of pre-product and deionized water is 1g:10mL~1g:20mL.Recycle calcium chloride solution energy reuse In step S110.
Step S140, by pre-product using inorganic acid immersion 12 it is small when~24 it is small when, then with 70 DEG C~80 DEG C of washing Wash to neutrality and obtain multiporous biological matter carbon.
In one of the embodiments, inorganic acid is selected from least one of hydrochloric acid, sulfuric acid and nitric acid, is preferably salt Acid.
In one of the embodiments, the concentration of inorganic acid is 2mol/L~6mol/L.
In one of the embodiments, pre-product and inorganic acid solid-to-liquid ratio are 1g:10mL~1g:20mL.
In one of the embodiments, separation of solid and liquid obtains solid after pre-product is soaked using inorganic acid, then with 70 DEG C~80 DEG C of water washing solid.
In one of the embodiments, when using inorganic acid immersion 24 small pre-product.
Step S150, ground after multiporous biological matter carbon is dried.
In one of the embodiments, multiporous biological matter carbon is dried at 60 DEG C~70 DEG C and processing is dried.It is preferred that , the constant temperature drying at 60 DEG C.
In one of the embodiments, multiporous biological matter carbon is placed in baking oven and processing is dried.
In one of the embodiments, multiporous biological matter carbon is ground using agate mortar, the time of milled processed For 0.2 it is small when~0.6 it is small when.
In one of the embodiments, multiporous biological matter carbon is ground until the particle diameter of multiporous biological matter carbon is 800 Micron~900 microns.
The preparation method of above-mentioned multiporous biological matter carbon, has the following advantages:
(1), it is cheap and easy to get using stalk as carbon source, resource reutilization is realized, reduces environmental pollution, is solved discarded Crops deal with the problem of environmental pollution of generation improperly, also achieve maximally utilizing for resource, reduce multiporous biological matter carbon Manufacturing cost;
(2), using can be cheap using the calcium chloride of circulation and stress as activator, production cost be reduced;
(3), the multiporous biological matter carbon of preparation can be easily controlled by the concentration and dosage that adjust calcium chloride solution Pore size;
(4), calcium chloride has good flame retardant effect, in straw-carbonized and activated process, can effectively prevent red-hot The oxidation of charcoal, can improve the yield of activated carbon;
(5), negative material of the multiporous biological matter carbon prepared as lithium ion battery, can improve the electric discharge of lithium ion battery Specific capacity and cyclical stability.
The multiporous biological matter carbon of one embodiment, is prepared by the preparation method of above-mentioned multiporous biological matter carbon.
In one of the embodiments, the specific surface area of multiporous biological matter carbon is 237.2m2/ g~370.6m2/g。
In one of the embodiments, the porosity of multiporous biological matter carbon is 61%~70%.
In one of the embodiments, the aperture of multiporous biological matter carbon is 7.24%~9.65%.
Negative material of the above-mentioned multiporous biological matter carbon as lithium ion battery, can improve the specific discharge capacity of lithium ion battery And cyclical stability, its specific discharge capacity can reach 646 every gram of milliampere hour after 100 circulations, hold far more than the theory of graphite Amount;Operating voltage lies prostrate for 0-3, and operating temperature range is subzero 25 DEG C to 60 DEG C, and specific discharge capacity is high, and self-discharge rate is low.
The application of above-mentioned multiporous biological matter carbon in the battery.
In one of the embodiments, battery is lithium ion battery.
In one of the embodiments, negative material of the multiporous biological matter carbon as lithium ion battery.
Above-mentioned multiporous biological matter carbon is applied to battery, can propose specific discharge capacity and the circulation of battery especially lithium ion battery Stability.
Illustrated below in conjunction with specific embodiment.
Embodiment 1
The preparation of multiporous biological matter carbon comprises the following steps:
It is powder by corn straw smashing, 20 grams of maize straw powders and the calcium chloride solution of 200 milliliters of 3mol/L is mixed Close uniformly, when standing 24 is small at room temperature;
Freeze-day with constant temperature at mixture in an oven 60 DEG C is placed in crucible with cover, with 10 DEG C/min's in Muffle furnace Heating rate is heated to 300 DEG C, carries out obtaining cryogenic carbon compound when low-temperature carbonization 3 is small;
Cryogenic carbon compound is continued to be heated to 600 DEG C of progress high-temperature activations in Muffle furnace with the heating rate of 10 DEG C/min 2 it is small when, cooled to room temperature obtains pre-product.The deionized water that pre-product is put into addition 100mL in beaker washs to obtain Recycle calcium chloride solution;
By pre-product with the hydrochloric acid solution of 100mL2mol/L immersion 24 it is small when, then with 70 DEG C of deionized water be washed till neutrality, In an oven at 60 DEG C after freeze-day with constant temperature using agate mortar grinding 0.5 it is small when, you can obtain multiporous biological matter carbon.
Embodiment 2
The preparation of multiporous biological matter carbon comprises the following steps:
It is powder by corn straw smashing, 10 grams of maize straw powders and the calcium chloride solution of 200 milliliters of 2mol/L is mixed Close uniformly, when standing 24 is small at room temperature;
Freeze-day with constant temperature at mixture in an oven 60 DEG C is placed in crucible with cover, with 9 DEG C/min's in Muffle furnace Heating rate is heated to 300 DEG C, carries out obtaining cryogenic carbon compound when low-temperature carbonization 3 is small;
Cryogenic carbon compound is continued to be heated to 500 DEG C of progress high-temperature activations 1 in Muffle furnace with the heating rate of 9 DEG C/min Hour, cooled to room temperature obtains pre-product.The deionized water that pre-product is put into addition 100mL in beaker is washed back Receive calcium chloride solution;
By pre-product with the hydrochloric acid solution of 100mL4mol/L immersion 24 it is small when, then with 80 DEG C of deionized water be washed till neutrality, In an oven at 60 DEG C after freeze-day with constant temperature using agate mortar grinding 0.3 it is small when, you can obtain multiporous biological matter carbon.
Embodiment 3
The preparation of multiporous biological matter carbon comprises the following steps:
It is powder by corn straw smashing, 30 grams of maize straw powders and the calcium chloride solution of 200 milliliters of 4mol/L is mixed Close uniformly, when standing 12 is small at room temperature;
Freeze-day with constant temperature at mixture in an oven 65 DEG C is placed in crucible with cover, with 8 DEG C/min's in Muffle furnace Heating rate is heated to 350 DEG C, carries out obtaining cryogenic carbon compound when low-temperature carbonization 2 is small;
Cryogenic carbon compound is continued to be heated to 700 DEG C of progress high-temperature activations 3 in Muffle furnace with the heating rate of 8 DEG C/min Hour, cooled to room temperature obtains pre-product.The deionized water that pre-product is put into addition 100mL in beaker is washed back Receive calcium chloride solution;
By pre-product with the hydrochloric acid solution of 100mL6mol/L immersion 12 it is small when, then with 70 DEG C of deionized water be washed till neutrality, In an oven at 70 DEG C after freeze-day with constant temperature using agate mortar grinding 0.4 it is small when, you can obtain multiporous biological matter carbon.
Embodiment 4
The preparation of multiporous biological matter carbon comprises the following steps:
It is powder by corn straw smashing, 20 grams of maize straw powders and the calcium chloride solution of 200 milliliters of 2mol/L is mixed Close uniformly, when standing 16 is small at room temperature;
Freeze-day with constant temperature at mixture in an oven 60 DEG C is placed in crucible with cover, with 9 DEG C/min's in Muffle furnace Heating rate is heated to 330 DEG C, carries out obtaining cryogenic carbon compound when low-temperature carbonization 2 is small;
Cryogenic carbon compound is continued to be heated to 700 DEG C of progress high-temperature activations 2 in Muffle furnace with the heating rate of 9 DEG C/min Hour, cooled to room temperature obtains pre-product.The deionized water that pre-product is put into addition 100mL in beaker is washed back Receive calcium chloride solution;
By pre-product with the hydrochloric acid solution of 100mL2mol/L immersion 16 it is small when, then with 75 DEG C of deionized water be washed till neutrality, In an oven at 60 DEG C after freeze-day with constant temperature using agate mortar grinding 0.6 it is small when, you can obtain multiporous biological matter carbon.
Embodiment 5
The preparation of multiporous biological matter carbon comprises the following steps:
It is powder by corn straw smashing, 20 grams of maize straw powders and the calcium chloride solution of 200 milliliters of 4mol/L is mixed Close uniformly, when standing 20 is small at room temperature;
Freeze-day with constant temperature at mixture in an oven 70 DEG C is placed in crucible with cover, with 10 DEG C/min's in Muffle furnace Heating rate is heated to 340 DEG C, carries out obtaining cryogenic carbon compound when low-temperature carbonization 2.5 is small;
Cryogenic carbon compound is continued to be heated to 600 DEG C of progress high-temperature activations in Muffle furnace with the heating rate of 10 DEG C/min 3 it is small when, cooled to room temperature obtains pre-product.The deionized water that pre-product is put into addition 100mL in beaker washs to obtain Recycle calcium chloride solution;
By pre-product with the hydrochloric acid solution of 100mL6mol/L immersion 20 it is small when, then with 75 DEG C of deionized water be washed till neutrality, In an oven at 60 DEG C after freeze-day with constant temperature using agate mortar grinding 0.2 it is small when, you can obtain multiporous biological matter carbon.
Comparative example 1
The preparation of biomass carbon comprises the following steps:
It is powder by corn straw smashing, 20g maize straw powders is placed in crucible with cover, with 10 in Muffle furnace DEG C/heating rate of min is heated to 300 DEG C, carry out obtaining cryogenic carbon compound when low-temperature carbonization 3 is small;
By cryogenic carbon compound in Muffle furnace with the heating rate of 10 DEG C/min continue to be heated to 600 DEG C of insulations 2 it is small when, from So it is cooled to room temperature to obtain pre-product.
By pre-product with the hydrochloric acid solution of 100mL2mol/L immersion 24 it is small when, then with 70 DEG C of deionized water be washed till neutrality, In an oven at 60 DEG C after freeze-day with constant temperature using agate mortar grinding 0.5 it is small when, you can obtain biomass carbon.
Comparative example 2
It is powder by corn straw smashing, 20g maize straw powders is placed in crucible with cover, with 10 in Muffle furnace DEG C/heating rate of min is heated to 300 DEG C, carry out obtaining cryogenic carbon compound when low-temperature carbonization 3 is small;
Cryogenic carbon compound is uniformly mixed with the calcium chloride solution of 200 milliliters of 3mol/L, when standing 24 is small at room temperature;
After freeze-day with constant temperature at mixture in an oven 60 DEG C, continue to add with the heating rate of 10 DEG C/min in Muffle furnace When hot to 600 DEG C progress high-temperature activations 2 are small, cooled to room temperature obtains pre-product.Pre-product is put into beaker and is added The deionized water washing of 100mL is recycled calcium chloride solution;
By pre-product with the hydrochloric acid solution of 100mL2mol/L immersion 24 it is small when, then with 70 DEG C of deionized water be washed till neutrality, In an oven at 60 DEG C after freeze-day with constant temperature using agate mortar grinding 0.5 it is small when, you can obtain multiporous biological matter carbon.
Please refer to Fig. 1 to Fig. 2, Fig. 1 is the scanning electricity that multiporous biological matter carbon prepared by embodiment 1 amplifies 80000 times Sub- microphotograph, Fig. 2 are the transmission electron microscope photo that multiporous biological matter carbon prepared by embodiment 1 amplifies 30000 times.
It can be seen that the multiporous biological matter carbon of preparation from Fig. 1~Fig. 2, material structure becomes loose, has abundant hole knot Structure.
Tested by the specific surface area of the BET multiporous biological matter carbon obtained to embodiment 1~5 and comparative example 1~2, Tested by the porosity of the BJH multiporous biological matter carbon obtained to embodiment 1~5 and comparative example 1~2, the results are shown in Table 1.
Table 1
Item Specific surface area (m2/g) Porosity
Embodiment 1 370.6 70%
Embodiment 2 365.4 68%
Embodiment 3 287.2 61%
Embodiment 4 273.8 65%
Embodiment 5 365.5 63%
Comparative example 1 45 8%
Comparative example 2 187.1 47.3%
The multiporous biological matter carbon of embodiment 1, comparative example 1, comparative example 2 is applied to lithium ion battery and carries out charge and discharge electrical measurement Examination.
During charge-discharge test, by multiporous biological matter carbon and acetylene black, PVDF according to mass ratio 8:1:1 ratio is uniformly mixed Mixture is obtained, is allowed to form uniformly mixed slurry then to when NMP and small stirring 6 being added dropwise in mixture, slurry is uniform It is coated on copper foil and when 120 DEG C of dryings 12 of vacuum drying chamber are small, copper foil is struck out into the milli of diameter 12 using press machine after drying The sequin of rice.The anode of lithium ion battery is made with this, in the lithium ion battery applied to model CR2025 types.Its In, it is EC/DMC (1 to electrode, membrane PP, electrolyte to use lithium piece to be used as in the lithium ion battery of model CR2025 types: 1).Charge-discharge test is carried out to lithium ion battery.
Tested in blue electricity CT2001A multi-channel battery test systems under the current density of 0.2C, final voltage model Enclose for 0.02-3.0V, using the multiporous biological matter carbon of embodiment 1 lithium ion battery cycle performance figure as shown in figs. 34, Using the biomass carbon of comparative example 1 lithium ion battery cycle performance figure as shown in Fig. 5~6, use the porous life of comparative example 2 The cycle performance figure of the lithium ion battery of material carbon is as shown in Fig. 7~8.
Negative material of the multiporous biological matter carbon of embodiment 1 as lithium ion battery, 0.2C are can be seen that from Fig. 3 and Fig. 4 Current density under after charge and discharge cycles 100 times, specific discharge capacity reaches 646 every gram of milliampere hour, and charge specific capacity reaches 632.6 Every gram of milliampere hour;Negative material of the biomass carbon of comparative example 1 as lithium ion battery, under the current density of 0.2C discharge and recharge follow After ring 100 times, specific discharge capacity is 146.1 every gram of milliampere hour, and charge specific capacity reaches 145.5 every gram of milliampere hour;Comparative example 2 Negative material of the multiporous biological matter carbon as lithium ion battery, under the current density of 0.2C after charge and discharge cycles 100 times, discharge ratio Capacity reaches 225.2 every gram of milliampere hour, and charge specific capacity reaches 226.6 every gram of milliampere hour.
It can be seen that biomass of the multiporous biological matter carbon phase for comparative example 1 and comparative example 2 of embodiment 1 from Fig. 3~Fig. 8 Negative material of the carbon as lithium ion battery, has the charging and discharging capacity of higher.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, its description is more specific and detailed, but simultaneously Cannot therefore it be construed as limiting the scope of the patent.It should be pointed out that come for those of ordinary skill in the art Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (10)

1. a kind of preparation method of multiporous biological matter carbon, it is characterised in that comprise the following steps:
Stood after stalk is mixed with calcium chloride solution 12 it is small when~24 it is small when obtain mixture, wherein the stalk and the chlorine The mass ratio for changing the calcium chloride in calcium solution is 1:1.5~1:3;
By the mixture be dried processing after at 300 DEG C~350 DEG C low-temperature carbonization processing 2 it is small when~3 it is small when obtain it is low Warm carbide;
By the cryogenic carbon compound be heated to 500 DEG C~700 DEG C carry out high-temperature activations processing 1 it is small when~3 it is small when obtain pre-product; And
By the pre-product using inorganic acid immersion 12 it is small when~24 it is small when, then with 70 DEG C~80 DEG C of water washing to neutral To multiporous biological matter carbon.
2. the preparation method of multiporous biological matter carbon according to claim 1, it is characterised in that the stalk is corn stalk Stalk;And/or
The stalk is powdered.
3. the preparation method of multiporous biological matter carbon according to claim 1, it is characterised in that the inorganic acid is selected from salt At least one of acid, sulfuric acid and nitric acid.
4. the preparation method of multiporous biological matter carbon according to claim 1, it is characterised in that the concentration of the inorganic acid For 2mol/L~6mol/L.
5. the preparation method of multiporous biological matter carbon according to claim 4, it is characterised in that the pre-product and the nothing Machine strong acid solid-to-liquid ratio is 1g:10mL~1g:20mL.
6. the preparation method of multiporous biological matter carbon according to claim 1, it is characterised in that it is described by the mixture into When low-temperature carbonization processing 2 is small at 300 DEG C~350 DEG C after row drying process~3 it is small when the step of obtaining cryogenic carbon compound in, will The mixture dries at 60 DEG C~70 DEG C and processing is dried.
7. the preparation method of multiporous biological matter carbon according to claim 1, it is characterised in that described by the pre-product Using inorganic acid immersion 12 it is small when~24 it is small when the step of before, further include step:Using pre-product described in water washing, obtain Recycle calcium chloride solution.
8. the preparation method of multiporous biological matter carbon according to claim 1, it is characterised in that further include step:By described in Ground after the drying of multiporous biological matter carbon.
9. the multiporous biological matter carbon obtained by the preparation method of claim 1~8 any one of them multiporous biological matter carbon.
10. the application of multiporous biological matter carbon in the battery described in claim 9.
CN201711285423.2A 2017-12-07 2017-12-07 Preparation method of porous biomass carbon, porous biomass carbon and application Active CN108033447B (en)

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CN108424303A (en) * 2018-06-11 2018-08-21 孙永妮 A method of preparing pest-resistant organic composite fertilizer using agriculture wastes
CN109734473A (en) * 2019-03-11 2019-05-10 福州大学 A kind of porous ceramics and preparation method thereof
CN111408348A (en) * 2020-04-28 2020-07-14 南阳师范学院 Preparation method of straw-based porous biochar nanospheres
CN111864206A (en) * 2019-04-30 2020-10-30 贝特瑞新材料集团股份有限公司 Hard carbon negative electrode material, preparation method thereof, pole piece comprising hard carbon negative electrode material and lithium ion battery
CN113247985A (en) * 2021-07-09 2021-08-13 生态环境部华南环境科学研究所 TBBPA-containing sewage treatment method, porous carbon microsphere material and preparation method
CN113381014A (en) * 2021-06-08 2021-09-10 西安亚弘泰新能源科技有限公司 Preparation method of ultralow-temperature lithium ion battery negative electrode material
CN113713771A (en) * 2021-09-29 2021-11-30 长春工业大学 Method for preparing adsorbing material and pentosan through biomass catalysis hydrothermal method

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GB125230A (en) * 1918-04-16 1919-04-16 Tai Koo Sugar Refining Company Improved Process for the Production of Decolourizing Carbon.
CN1245776A (en) * 1999-08-31 2000-03-01 林天安 Method for preparing vehicular active carbon by using straw stalks and saw dust
CN103213982A (en) * 2013-04-28 2013-07-24 广西大学 Method for preparing activated carbon by carrying out microwave irradiation on banana straws
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CN108424303A (en) * 2018-06-11 2018-08-21 孙永妮 A method of preparing pest-resistant organic composite fertilizer using agriculture wastes
CN109734473A (en) * 2019-03-11 2019-05-10 福州大学 A kind of porous ceramics and preparation method thereof
CN109734473B (en) * 2019-03-11 2021-09-28 福州大学 Porous ceramic and preparation method thereof
CN111864206A (en) * 2019-04-30 2020-10-30 贝特瑞新材料集团股份有限公司 Hard carbon negative electrode material, preparation method thereof, pole piece comprising hard carbon negative electrode material and lithium ion battery
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CN111408348A (en) * 2020-04-28 2020-07-14 南阳师范学院 Preparation method of straw-based porous biochar nanospheres
CN113381014A (en) * 2021-06-08 2021-09-10 西安亚弘泰新能源科技有限公司 Preparation method of ultralow-temperature lithium ion battery negative electrode material
CN113381014B (en) * 2021-06-08 2023-03-03 西安亚弘泰新能源科技有限公司 Preparation method of ultralow-temperature lithium ion battery negative electrode material
CN113247985A (en) * 2021-07-09 2021-08-13 生态环境部华南环境科学研究所 TBBPA-containing sewage treatment method, porous carbon microsphere material and preparation method
CN113713771A (en) * 2021-09-29 2021-11-30 长春工业大学 Method for preparing adsorbing material and pentosan through biomass catalysis hydrothermal method

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