CN106744798B - A kind of method and its application preparing hard carbon using carbon containing biological mass shell - Google Patents
A kind of method and its application preparing hard carbon using carbon containing biological mass shell Download PDFInfo
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- CN106744798B CN106744798B CN201611140134.9A CN201611140134A CN106744798B CN 106744798 B CN106744798 B CN 106744798B CN 201611140134 A CN201611140134 A CN 201611140134A CN 106744798 B CN106744798 B CN 106744798B
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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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of methods for preparing hard carbon using carbon containing biological mass shell, include the following steps: according to the alkali in alkaline solution: the mass ratio of carbon containing biology mass shell powder is (1-20): 1 amount, carbon containing biological mass shell powder is added into alkaline solution, is denoted as solution A；Solution A is injected in stainless steel cauldron and seals hydro-thermal, is taken out after product cools to room temperature with the furnace, pretreated carbon containing biological mass shell powder is obtained；Enough acid cleaning is added in the carbon containing biological mass shell powder of obtained pretreatment, and removes extra inorganic salt impurities ion, obtains hard carbon presoma；Obtained hard carbon presoma is carbonized under inert gas atmosphere, obtains B substance；Obtained hard carbon material is first removed into silicon with enough acid, then is dried, hard carbon is obtained.The beneficial effects of the present invention are: having low in raw material price, enriching, industrialization degree is high, and manufacturing cost is low, is easy to commercially produce, have excellent performance, the high feature of practicability.
Description
Technical field
The present invention relates to a kind of method and its application that hard carbon is prepared using carbon containing biological mass shell.
Background technique
A large amount of burnings of conventional fossil fuel cause energy crisis and serious environmental pollution, and renewable and clean energy resource is opened
It sends out very urgent with utilization.However, though the new energy cleaning such as renewable and clean energy resource such as solar energy, wind energy is renewable,
It is influenced by period and weather etc. bigger, has the shortcomings that unstable, discontinuous and uncontrollable, need to develop matched storage
Energy device carrys out the stability to guarantee power generation, power supply.Compared with other electrochemical energy storages, lithium ion battery has energy
Metric density is big, have extended cycle life, operating voltage height, memory-less effect, the advantages that self discharge is small, operating temperature range is wide, just
It is very widely used to take formula electronic equipment, communication apparatus, static energy storage and electric car field.But in large-scale energy storage side
Face, lithium ion battery are faced with the problems such as at high cost, the service life is short, there are security risks, with lithium electricity industry development, to lithium
Demand it is increasing, and abundance of the lithium in the earth's crust is only 0.0065wt%, and is unevenly distributed, exploits difficulty, is thereby resulted in
Lithium cost increases, and is not able to satisfy the needs of increasingly developed energy-storage battery.
Sodium and lithium are in the same main group, and positioned at the lower section of lithium, therefore the physicochemical properties of the two are closely similar.With lithium
It compares, abundance of the sodium in the earth's crust is 2.74wt%, and resourceful, exploitation is convenient, it is low in cost, it is highly-safe.Meanwhile sodium from
Sub- battery energy density is high, at low cost, non-environmental-pollution, is very suitable for extensive stored energy application.Electrode material is sodium ion
The important component of battery.By the end of currently, a series of development of positive electrodes has made high-performance sodium-ion battery
Using being possibly realized.Finding suitable anode material of lithium-ion battery is still a great challenge.Graphite is with its work electricity
The low, good cycling stability in position, excellent conductivity and it is cheap many advantages, such as, be always lithium ion battery negative material
Mainstream.However, embedding sodium capacity of the graphite in traditional lipid electrolyte is but very low (35mAh/g) due to thermodynamic one.Its
His sodium cell negative pole material such as alloy, oxide, organic compound etc. is there are structure collapses, capacity is low, first effect is low, conductivity is low etc.
Problem, it is difficult to realize the application in lithium ion battery.Hard carbon anode material of lithium-ion battery reversible capacity height, charging/discharging voltage
Platform is low, cycle performance is excellent, is expected to the mainstream negative electrode material as sodium-ion battery.
The presoma of hard carbon mainly has high molecular polymer, the hard carbon being pyrolyzed using high molecular polymer, and performance is excellent
It is different but expensive, it is unfavorable to its commercialization in sodium-ion battery.
Summary of the invention
Technical problem to be solved by the invention is to provide it is a kind of using carbon containing biological mass shell prepare hard carbon method and its
Using to overcome the deficiencies in the prior art described above.
The technical scheme to solve the above technical problems is that a kind of side for preparing hard carbon using carbon containing biological mass shell
Method includes the following steps:
Step 1: according to the alkali in alkaline solution: the mass ratio of carbon containing biology mass shell powder is (1-20): 1 amount, to alkali
Property solution in carbon containing biological mass shell powder is added, be denoted as solution A；
Step 2: solution A is injected in stainless steel cauldron, in 30 DEG C to 200 DEG C sealing hydro-thermal 1h to 20h, to product
It is taken out after cooling to room temperature with the furnace, obtains pretreated carbon containing biological mass shell powder；
Step 3: the carbon containing biological mass shell powder of pretreatment obtained in step 2 is added enough acid cleaning, then with pure
Water washing removes extra inorganic salt impurities ion to neutrality, obtains hard carbon presoma；
Step 4: under inert gas atmosphere by hard carbon presoma obtained in step 3, being carbonized in 800 DEG C to 1500 DEG C
2h to 10h obtains B substance；
Step 5: B substance obtained in step 4 is first removed silicon with enough acid, then it is washed till neutrality with a large amount of clear water,
It is finally dried, obtains hard carbon.
A kind of application of the hard carbon as sodium-ion battery cathode material.
The beneficial effects of the present invention are: having low in raw material price, enriching, industrialization degree is high, and manufacturing cost is low, is easy to
It commercially produces, has excellent performance, the high feature of practicability.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph using the preparation-obtained hard carbon of the method for the invention；
Fig. 2 is the circulation tested after anode material of lithium-ion battery is made using the preparation-obtained hard carbon of the present invention
Figure；
Fig. 3 is the charging and discharging curve of obtained sodium-ion battery.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
Embodiment one, as shown in Figure 1, a kind of method for preparing hard carbon using carbon containing biological mass shell, includes the following steps:
S01, it weighs 20g mangosteen shell and is crushed with pulverizer, obtain mangosteen shell powder, and obtained mangosteen shell powder is uniform
It is dispersed in the sodium hydroxide solution that 100mL is 0.2M to 2M to 200mL concentration, wherein the concentration of sodium hydroxide solution is optional
For 0.2M, 0.4M, 0.7M, 0.82M, 0.9M, 1.2M, 1.43M, 1.7M, 1.9M, 2.0M, due to using mangosteen shell, by mountain
The influence of bamboo shell self-molecules present composition, the concentration of sodium hydroxide solution is preferably 0.9M, obtains solution A；
S02, solution A is injected in stainless steel cauldron, in 120 DEG C to 180 DEG C sealing hydro-thermal 6h to 12h, the temperature of hydro-thermal
Degree can be 30 DEG C, 120 DEG C, 126.2 DEG C, 130.7 DEG C, 144.1 DEG C, 159.5 DEG C, 167.8 DEG C, 173.4 DEG C, 180 DEG C, 200 DEG C,
According to the concentration of preferred sodium hydroxide solution, obtained at this concentration by testing repeatedly, the temperature of hydro-thermal reaction it is optimal
Value is 144.1 DEG C, at this point, reacting between mangosteen shell and sodium hydroxide is the most active, the hydro-thermal time can for 1h, 6h, 6.5h,
7.2h, 8.4h, 9.6h, 10.1h, 11.7h, 12h, 20h, but according to the concentration and hydro-thermal of optimal sodium hydroxide solution
Temperature, by test repeatedly obtain this concentration and at a temperature of, hydro-thermal time optimal be 10.1h, cool to room with the furnace to product
It is taken out after temperature, obtains pretreated mangosteen shell powder；
S03, it enough dilute hydrochloric acid is added in pretreated mangosteen shell powder obtained in S02 cleans, then with pure water washing
To neutrality, and extra inorganic salt impurities ion is removed, obtains hard carbon presoma；
S04, by hard carbon presoma obtained in S03 in N2Or under Ar atmosphere, in 800 DEG C to 1500 DEG C carbonization 2h to 10h,
The temperature of carbonization can be 800 DEG C, 924 DEG C, 1011 DEG C, 1147 DEG C, 1265 DEG C, 1371 DEG C, 1424 DEG C, 1500 DEG C, by repeatedly
Experiment show that hard carbon presoma obtained by mangosteen shell in the Optimal Temperature value being carbonized is 1265 DEG C, and carbonization time can be
2h, 3.2h, 4.7h, 6.1h, 7.4h, 8.6h, 9.3,10h obtain according to optimal carburizing temperature by testing repeatedly, herein
At a temperature of carbonization time it is optimal be 7.4h, obtain B substance；
S05, B substance obtained in S04 is first removed into silicon with enough hydrofluoric acid, is then washed till again with a large amount of clear water
Property, it is finally dried, obtains hard carbon.
Embodiment two: as shown in Figure 1, a kind of method for preparing hard carbon using carbon containing biological mass shell, includes the following steps:
S01, it weighs 20g walnut shell and is crushed with pulverizer, obtain walnut shell powder, and obtained walnut shell powder is uniform
It is dispersed in the sodium hydroxide solution that 100mL is 0.2M to 2M to 200mL concentration, wherein the concentration of sodium hydroxide solution is optional
For 0.2M, 0.4M, 0.7M, 0.82M, 0.9M, 1.2M, 1.43M, 1.7M, 1.9M, 2.0M, due to using walnut shell, by core
The influence of peach shell self-molecules present composition, the concentration of sodium hydroxide solution is preferably 1.2M, obtains solution A；
S02, solution A is injected in stainless steel cauldron, in 120 DEG C to 180 DEG C sealing hydro-thermal 6h to 12h, the temperature of hydro-thermal
Degree can be 30 DEG C, 120 DEG C, 126.2 DEG C, 130.7 DEG C, 144.1 DEG C, 159.5 DEG C, 167.8 DEG C, 173.4 DEG C, 180 DEG C, 200 DEG C,
According to the concentration of preferred sodium hydroxide solution, obtained at this concentration by testing repeatedly, the temperature of hydro-thermal reaction it is optimal
Value is 126.2 DEG C, at this point, reacting between mangosteen shell and sodium hydroxide is the most active, the hydro-thermal time can for 1h, 6h, 6.5h,
7.2h, 8.4h, 9.6h, 10.1h, 11.7h, 12h, 20h, but according to the concentration and hydro-thermal of optimal sodium hydroxide solution
Temperature, by test repeatedly obtain this concentration and at a temperature of, hydro-thermal time optimal be 11.7h, cool to room with the furnace to product
It is taken out after temperature, obtains pretreated walnut shell powder；
S03, it enough dilute hydrochloric acid is added in pretreated walnut shell powder obtained in S02 cleans, then with pure water washing
To neutrality, and extra inorganic salt impurities ion is removed, obtains hard carbon presoma；
S04, by hard carbon presoma obtained in S03 in N2Or under Ar atmosphere, in 800 DEG C to 1500 DEG C carbonization 2h to 10h,
The temperature of carbonization can be 800 DEG C, 924 DEG C, 1011 DEG C, 1147 DEG C, 1265 DEG C, 1371 DEG C, 1424 DEG C, 1500 DEG C, by repeatedly
Experiment show that hard carbon presoma obtained by walnut shell in the Optimal Temperature value being carbonized is 1424 DEG C, and carbonization time can be
2h, 3.2h, 4.7h, 6.1h, 7.4h, 8.6h, 9.3h, 10h obtain according to optimal carburizing temperature by testing repeatedly, herein
At a temperature of carbonization time it is optimal be 8.6h, obtain B substance；
S05, B substance obtained in S04 is first removed into silicon with enough hydrofluoric acid, is then washed till again with a large amount of clear water
Property, it is finally dried, obtains hard carbon.
When raw material is mangosteen shell, after the temperature of hydro-thermal reaction is to final gained hard carbon for the first time specific capacity and circulation 100 times
The influence of specific capacity obtains following data by testing repeatedly, as shown in table 1:
Table 1
When raw material is walnut shell, after the temperature of hydro-thermal reaction is to final gained hard carbon for the first time specific capacity and circulation 100 times
The influence of specific capacity obtains following data by testing repeatedly, as shown in table 2:
Table 2
The obtained hard carbon of embodiment one or two is prepared into anode material of lithium-ion battery, and carries out experimental test, institute
The data measured are as shown in Figure 2 and Figure 3, and after 150mA/g current density recycles 100 times, specific capacity is about 320mAhg-1.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (5)
1. a kind of method for preparing hard carbon using carbon containing biological mass shell, which comprises the steps of:
Step 1: according to the alkali in alkaline solution: the mass ratio of mangosteen shell or walnut shell powder is (1-20): 1 amount, to alkalinity
Mangosteen shell or walnut shell powder are added in solution, is denoted as solution A；
Step 2: solution A is injected in stainless steel cauldron, in 120 DEG C to 180 DEG C sealing hydro-thermal 6h to 12h, to product with furnace
It is taken out after being cooled to room temperature, obtains pretreated mangosteen shell or walnut shell powder；
Step 3: enough acid cleaning is added in pretreatment mangosteen shell obtained in step 2 or walnut shell powder, then use pure water
It washs to neutrality, and removes extra inorganic salt impurities ion, obtain hard carbon presoma；
Step 4: under inert gas atmosphere by hard carbon presoma obtained in step 3, being arrived in 800 DEG C to 1500 DEG C carbonization 2h
10h obtains B substance；
Step 5: B substance obtained in step 4 is first removed silicon with enough acid, then it is washed till neutrality with a large amount of clear water, finally
It is dried, obtains hard carbon.
2. a kind of method for preparing hard carbon using carbon containing biological mass shell according to claim 1, which is characterized in that the step
In rapid one, the alkali is sodium hydroxide.
3. a kind of method for preparing hard carbon using carbon containing biological mass shell according to claim 1, which is characterized in that the step
In rapid three, used acid is dilute hydrochloric acid.
4. a kind of method for preparing hard carbon using carbon containing biological mass shell according to claim 1, which is characterized in that the step
In rapid four, the inert gas atmosphere includes N2Or Ar.
5. a kind of application to 4 any hard carbons as sodium-ion battery cathode material according to claim 1.
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| CN107681137B (en) * | 2017-09-20 | 2020-11-24 | 齐鲁工业大学 | Sodium ion battery C/C70/CaS composite negative electrode material and preparation method thereof |
| CN107879323A (en) * | 2017-11-15 | 2018-04-06 | 上海空间电源研究所 | A kind of hard carbon material and its preparation method and application |
| CN108682815B (en) * | 2018-05-11 | 2020-12-01 | 浙江大学 | Efficient hard carbon material and preparation method and application thereof |
| CN109467068A (en) * | 2018-11-01 | 2019-03-15 | 南昌航空大学 | A kind of preparation method of biological material Ba Danmu base porous carbon materials and its application in terms of anode of microbial fuel cell |
| GB201905044D0 (en) * | 2019-04-09 | 2019-05-22 | Faradion Ltd | Hard carbon-containing materials |
| CN114864934A (en) * | 2022-04-11 | 2022-08-05 | 温州大学碳中和技术创新研究院 | Preparation method and application of hazelnut shell hard carbon material for sodium ion battery cathode |
| CN116314730B (en) * | 2023-05-22 | 2023-07-28 | 江苏传艺科技股份有限公司 | Preparation method of biomass-based carbon electrode material for sodium ion battery |
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