CN109786723A - A kind of preparation method of the carbon composite of three-dimensional porous low metal doping - Google Patents
A kind of preparation method of the carbon composite of three-dimensional porous low metal doping Download PDFInfo
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- CN109786723A CN109786723A CN201910180007.9A CN201910180007A CN109786723A CN 109786723 A CN109786723 A CN 109786723A CN 201910180007 A CN201910180007 A CN 201910180007A CN 109786723 A CN109786723 A CN 109786723A
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- carbon composite
- dimensional porous
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- low metal
- metal doping
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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 provides a kind of preparation methods of the carbon composite of three-dimensional porous low metal doping, it is characterized in that, include: step 1: the pretreated step of radish: white radishes being cleaned, peeling is sliced, freeze-drying, it is immersed in metal ion precursor solution after grinding, soaking time be 5~for 24 hours, then the sample after immersion is collected by centrifugation, is then dried;Step 2: the material being dried to obtain being placed in tube furnace, then 300~1000 DEG C of heat preservations 1~for 24 hours under the atmosphere of nitrogen are down to room temperature, grinding is collected;Step 3: it is in mass ratio that the mixing of 1:2~7 activates, then deionized water is washed till neutrality by material and potassium hydroxide that step 2 is collected, it is dry to collect to get the carbon composite adulterated to three-dimensional porous low metal.Shape characteristic of the present invention is in uniformly rule, and transition metal, oxygen and carbon atom are evenly distributed on material, and preparation process is simple, and cost is relatively low and scientific research value with higher.
Description
Technical field
The invention belongs to materialogy fields, are related to a kind of lithium ion battery negative material, specifically a kind of porous low
The preparation method of metal-doped biomass carbon composite material.
Background technique
Currently, about 80% energy consumption depends on the use of non-renewable energy resources-fossil fuel, and which results in serious
Environment, weather and the problems such as health, therefore people gradually develop and use green energy resource, including solar energy, wind energy, tide energy etc.
The energy will become most promising selection in sustainable development economy.In addition, being one for the use of electric vehicle
The important channel to reduce environmental pollution.However efficient energy storage is then needed to set using solar energy and wind energy as electric car
Standby, in this respect, lithium ion battery (LIBs) then plays an important role, since lithium ion battery has high energy close
The advantages that degree, long cycle life and be widely used in portable electronic device, such as laptop, mobile phone and medical treatment
Equipment microelectronic device.However, lithium ion battery still suffers from many challenges in practical applications, for example improve power density
And energy density, the problems such as reducing the safety of cost and battery, to seriously restrict the extensive use of lithium ion battery.
Currently, commercialized anode of lithium ion battery (cathode) and cathode (anode) material are mainly by graphite, lithium metal oxide (lithium
Cobalt/cobalt oxide and lithium manganese oxide) and LiFePO4, wherein commercialized graphite electrode is since it is with preferable cycle performance
With high rate performance and it is cheap the advantages that and be widely used, but as people are to high-energy density and high power density
Demand constantly increase, commercialized graphite can no longer meet the needs of people, because graphite has lower theoretical specific volume
Measure (372mAh g-1), it is therefore desirable to continually look for the electrode material with higher theoretical specific capacity.With graphite-phase ratio, transition gold
Belong to one of the lithium ion battery negative material that oxide is considered as most future due to its theoretical specific capacity with higher,
However, transition metal oxide usually has poor stable circulation performance as lithium ion battery negative material, certainly due to it
The poor electric conductivity of body, slower kinetics and the electrode material serious volume expansion of charge and discharge process the problems such as
It is all serious to constrain the extensive use of transition metal oxide.
Summary of the invention
It is described the object of the present invention is to provide a kind of preparation method of the carbon composite of three-dimensional porous low metal doping
It is steady that the preparation method of the biomass carbon composite material of this three-dimensional porous low metal doping significantly improves lithium ion battery circulation
Qualitative poor problem and make full use of biological material that can reduce resource pressure.
In order to achieve the above object, the present invention provides a kind of preparations of the carbon composite of three-dimensional porous low metal doping
Method characterized by comprising
Step 1: the pretreated step of radish: radish is cleaned, and removes the peel, and is sliced, and freeze-drying is immersed in metal after grinding
In ion precursor solution, soaking time is 1~240h, is then collected by centrifugation, is then dried;
Step 2: the material that step 1 is dried to obtain is placed in tube furnace, 100~1000 DEG C of heat preservations under the atmosphere of nitrogen
1~for 24 hours, it is then down to room temperature, grinding is collected;
Step 3: being in mass ratio that the mixing of 1:2~7 activates, then spends by material and potassium hydroxide that step 2 is collected
Ion water washing is dry to collect to get the carbon composite adulterated to three-dimensional porous low metal to neutrality.
Preferably, the metal ion precursor solution is the transition metal salt solution of 0.1~10mol/L.
It is highly preferred that the transition metal salt is at least one of cobalt salt, zinc salt and nickel salt.
Preferably, the transition metal salt is at least one of cobalt nitrate, nickel nitrate and zinc nitrate.
Preferably, in the carbon composite of the described three-dimensional porous low metal doping, the atom doped amount of Co is 0.02~
0.08wt%.
Preferably, in the carbon composite of the described three-dimensional porous low metal doping, the atom doped amount of Ni is 0.02~
0.10wt%.
Preferably, in the carbon composite of the described three-dimensional porous low metal doping, the atom doped amount of Zn is 0.02~
0.10wt%.
Preferably, in the carbon composite of the described three-dimensional porous low metal doping, the atom doped amount of C is 70~
80wt%.
Preferably, in the carbon composite of the described three-dimensional porous low metal doping, O atom doping is 20~
30wt%.
Preferably, in the carbon composite of three-dimensional porous low metal doping, various elements are all uniformly distributed.
Preferably, the condition of the activation are as follows: activation temperature is 550-650 DEG C, activation time 1-3h.
Preferably, the condition of the activation are as follows: the material and solid potassium hydroxide of collection are mixed into mass ratio for 1:3
Row activation, 600 DEG C of high-temperature activation 2h.
Preferably, it in the step 2, is cooled to room temperature, with 0.08-0.12mol/L HCl treatment 3-8h, after drying,
Grinding collection is carried out again.
It is obtained by testing characterization, cobalt element is effectively entrained in biomass carbon substrate, while a variety of gold may be implemented
Belong to element doping, the present invention combination biomass carbon water suction dewatering Principle, successfully by metal-doped to inside biomass carbon, to have
Cyclical stability of the raising metal carbon composite of effect as lithium ion battery negative material.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is using radish as biomass carbon source, the porous carbon composite of synthesis low metal doping, and shape characteristic is in
Uniformly rule, transition metal, oxygen and carbon atom are evenly distributed on material, and preparation process is simple, and cost is relatively low and has
There is higher scientific research value.
The present invention utilizes plant cell water suction/dewatering Principle, and metal ion is successfully introduced into carbon substrate effectively to mention
The chemical property of high metal carbon composite.
Detailed description of the invention
Fig. 1 is the compound SEM figure of the biomass carbon of porous low metal doping;A~d is the life of three-dimensional porous low metal doping
SEM figure of the substance carbon composite under different resolution, shows and successfully prepares three-dimensional porous nano piece low metal and mix
Miscellaneous biomass carbon composite material;E~h is the Mapping figure of the biomass carbon composite material of three-dimensional porous low metal doping, can
To find out that Elements C, O, Co are uniformly distributed in the material;
Fig. 2 is Raman, FTIR, TGA and XRD diagram of the biomass carbon composite material of three-dimensional porous low metal doping;
Fig. 3 is the XPS figure of the biomass carbon composite material of three-dimensional porous low metal doping;
Fig. 4 is the chemical property figure of the biomass carbon composite material of three-dimensional porous low metal doping, and figure a-b is before activating
Constant current charge-discharge curve afterwards, c-d are respectively 100 and 1000mAh g in current density-1When cycle performance figure;
Fig. 5 is the chemical property figure of the biomass carbon composite material of three-dimensional porous low metal doping, schemes a for CV figure, schemes b
For AC impedance figure, the biomass carbon composite material activation front and back that c is pure radish sample and three-dimensional porous low metal is adulterated is schemed
Charge and discharge long circulating figure, figure d are pure radish sample and the biomass carbon composite material activation front and back that three-dimensional porous low metal is adulterated
High rate performance figure under different current densities, as can be seen from the figure final target product tool and pure radish and and work
Sample before change is greatly improved compared to chemical property.
Fig. 6 is preparation flow figure of the invention.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Used each raw material is commercial product in following embodiment.
Embodiment 1
As shown in fig. 6, a kind of preparation method of the carbon composite of three-dimensional porous low metal doping, contains Co, C, O member
Element, preparation method are as follows:
1) the pretreated step of radish: white radishes are cleaned, and are removed the peel, slice;- 48 DEG C of freeze-drying 72h prepare 5mol/L
Cobalt nitrate solution, after the radish after freeze-drying is then ground to 200~300 mesh, it is molten to be immersed in prepared cobalt nitrate
In liquid, soaking time is for 24 hours, then the carrot powder after immersion to be collected by centrifugation, then 60 DEG C of vacuum drying 12h;
2) three-dimensional porous low metal doped carbon composite material carbonization: the material obtained after drying is placed in tube furnace,
The lower 600 DEG C of heat preservations 2h of the atmosphere of nitrogen, then Temperature fall is down to room temperature, after 0.1mol/L HCl treatment 5h, 60 DEG C of drying
12h after being ground to 200~300 mesh, is collected;
3) the step of three-dimensional porous low metal doping carbon composite activation: the material and solid hydrogen-oxygen that step 2 is collected
Change potassium is that 1:3 is mixed in mass ratio, 600 DEG C of high-temperature activation 2h, then is washed with deionized water to neutrality, after 60 DEG C of vacuum drying 12h,
Grinding is collected to get to the carbon composite of three-dimensional porous low metal doping, by scanning electron microscope test, C atom
Content is about 78.27wt%, and the content of O atom is about 21.64wt%, and the content of Co atom is about 0.08wt%.
Fig. 1 is the compound SEM figure of the biomass carbon of porous low metal doping;A~d is the life of three-dimensional porous low metal doping
SEM figure of the substance carbon composite under different resolution, shows and successfully prepares three-dimensional porous nano piece low metal and mix
Miscellaneous biomass carbon composite material;E~h is the Mapping figure of the biomass carbon composite material of three-dimensional porous low metal doping, can
To find out that Elements C, O, Co are uniformly distributed in the material;
Fig. 2 is Raman, FTIR, TGA and XRD diagram of the biomass carbon composite material of three-dimensional porous low metal doping;
Fig. 3 is the XPS figure of the biomass carbon composite material of three-dimensional porous low metal doping;It can be seen that the material mainly by
C, tri- kinds of element compositions of O, Co.
Embodiment 2
The carbon composite for the three-dimensional porous low metal doping that embodiment 1 obtains is prepared into electrode slice, specific steps are as follows:
1) carbon composite, 12mg acetylene black and the 6mg of the three-dimensional porous low metal doping of the 42mg prepared embodiment 1
Binder PVDF 7:2:1 in mass ratio grinding is added 0.25mL NMP grinding and is slurried;
2) slurry of above-mentioned preparation is uniformly coated on copper foil with scraper, at 80 DEG C of one nights of vacuum drying, obtains electrode
Material.
Embodiment 3
2 obtained electrode material of embodiment is subjected to electrochemical property test:
2 obtained electrode material of embodiment is cut into pole piece, 2032 battery case is selected to be assembled in glove box.
Positive electrode is pole piece obtained in embodiment 2, and cathode is lithium piece, and electrolyte is the LiPF of 1M6(being dissolved in volume ratio is 1:1:
1 ethyl carbonate/dimethyl carbonate/diethyl carbonate).After assembled one night of battery standing, electricity is carried out with blue electric system
Chemical property test, as shown in Figure 4 and Figure 5.
Embodiment 4
A kind of preparation method of the carbon composite of three-dimensional porous low metal doping, contains Ni, C, O element, preparation side
Method are as follows:
1) the pretreated step of radish: white radishes are cleaned, and are removed the peel, slice;- 48 DEG C of freeze-drying 72h prepare 5mol/L
Nickel nitrate solution, after the radish after freeze-drying is then ground to 200~300 mesh, it is molten to be immersed in prepared nickel nitrate
In liquid, soaking time is for 24 hours, then the carrot powder after immersion to be collected by centrifugation, then 60 DEG C of vacuum drying 12h;
2) three-dimensional porous low metal doped carbon composite material carbonization: the material obtained after drying is placed in tube furnace,
The lower 600 DEG C of heat preservations 2h of the atmosphere of nitrogen, then Temperature fall is down to room temperature, after 0.1mol/L HCl treatment 5h, 60 DEG C of drying
12h after being ground to 200~300 mesh, is collected;
3) the step of three-dimensional porous low metal doping carbon composite activation: the material and solid hydrogen-oxygen that step 2 is collected
Change potassium is that 1:3 is mixed in mass ratio, 600 DEG C of high-temperature activation 2h, then is washed with deionized water to neutrality, after 60 DEG C of vacuum drying 12h,
Grinding is collected to get to the carbon composite of three-dimensional porous low metal doping, by scanning electron microscope test, C atom
Content is about 78.27wt%, and the content of O atom is about 21.64wt%, and the content of Ni atom is about 0.10wt%.
Embodiment 5
A kind of preparation method of the carbon composite of three-dimensional porous low metal doping, contains Zn, C, O element, preparation side
Method are as follows:
1) the pretreated step of radish: white radishes are cleaned, and are removed the peel, slice;- 48 DEG C of freeze-drying 72h prepare 5mol/L
Zinc nitrate solution, after the radish after freeze-drying is then ground to 200~300 mesh, it is molten to be immersed in prepared zinc nitrate
In liquid, soaking time is for 24 hours, then the carrot powder after immersion to be collected by centrifugation, then 60 DEG C of vacuum drying 12h;
2) three-dimensional porous low metal doped carbon composite material carbonization: the material obtained after drying is placed in tube furnace,
The lower 600 DEG C of heat preservations 2h of the atmosphere of nitrogen, then Temperature fall is down to room temperature, after 0.1mol/L HCl treatment 5h, 60 DEG C of drying
12h after being ground to 200~300 mesh, is collected;
3) the step of three-dimensional porous low metal doping carbon composite activation: the material and solid hydrogen-oxygen that step 2 is collected
Change potassium is that 1:3 is mixed in mass ratio, 600 DEG C of high-temperature activation 2h, then is washed with deionized water to neutrality, after 60 DEG C of vacuum drying 12h,
Grinding is collected to get to the carbon composite of three-dimensional porous low metal doping, by scanning electron microscope test, C atom
Content is about 78.27wt%, and the content of O atom is about 21.64wt%, and the content of Zn atom is about 0.10wt%.
Claims (10)
1. a kind of preparation method of the carbon composite of three-dimensional porous low metal doping characterized by comprising
Step 1: the pretreated step of radish: radish is cleaned, and removes the peel, and is sliced, and freeze-drying is immersed in metal ion after grinding
In precursor solution, soaking time is 1~240h, is then collected by centrifugation, is then dried;
Step 2: the material being dried to obtain is placed in tube furnace, under the atmosphere of nitrogen 100~1000 DEG C heat preservation 1~for 24 hours, so
After be down to room temperature, grinding is collected;
Step 3: it is in mass ratio that 1:2~7 is mixed and activated by material and potassium hydroxide that step 2 is collected, then deionized water
It is washed till neutrality, it is dry to collect to get the carbon composite adulterated to three-dimensional porous low metal.
2. the preparation method of the carbon composite of three-dimensional porous low metal doping as described in claim 1, which is characterized in that institute
The metal ion precursor solution stated is the transition metal salt solution of 0.1~10mol/L.
3. the preparation method of the carbon composite of three-dimensional porous low metal doping as claimed in claim 2, which is characterized in that institute
The transition metal salt stated is at least one of cobalt salt, zinc salt and nickel salt.
4. the preparation method of the carbon composite of three-dimensional porous low metal doping as described in claim 1, which is characterized in that institute
The transition metal salt stated is at least one of cobalt nitrate, nickel nitrate and zinc nitrate.
5. the preparation method of the carbon composite of three-dimensional porous low metal doping as described in claim 1, which is characterized in that institute
In the carbon composite for the three-dimensional porous low metal doping stated, the atom doped amount of Co is 0.02~0.08wt%.
6. the preparation method of the carbon composite of three-dimensional porous low metal doping as described in claim 1, which is characterized in that institute
In the carbon composite for the three-dimensional porous low metal doping stated, the atom doped amount of Ni is 0.02~0.10wt%.
7. the preparation method of the carbon composite of three-dimensional porous low metal doping as described in claim 1, which is characterized in that institute
In the carbon composite for the three-dimensional porous low metal doping stated, the atom doped amount of Zn is 0.02~0.10wt%.
8. the preparation method of the carbon composite of three-dimensional porous low metal doping as described in claim 1, which is characterized in that institute
In the carbon composite for the three-dimensional porous low metal doping stated, the atom doped amount of C is 70~80wt%.
9. the preparation method of the carbon composite of three-dimensional porous low metal doping as described in claim 1, which is characterized in that institute
In the carbon composite for the three-dimensional porous low metal doping stated, O atom doping is 20~30wt%.
10. the preparation method of the carbon composite of three-dimensional porous low metal doping as described in claim 1, which is characterized in that
The condition of the activation are as follows: the material and solid potassium hydroxide of collection are that 1:3 mixing is activated in mass ratio, 600 DEG C of height
Temperature activation 2h.
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CN110459772A (en) * | 2019-08-28 | 2019-11-15 | 浙江工业大学 | A kind of preparation method of the lead carbon composite for lead carbon battery cathode additive agent |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013139373A (en) * | 2011-12-28 | 2013-07-18 | Qinghua Univ | Method for producing graphene |
CN105923629A (en) * | 2016-04-26 | 2016-09-07 | 哈尔滨工程大学 | Method for preparing transition metal composite hetero atom doped porous carbon material through dipping, recrystallizing and carbonizing biomasses |
CN106927463A (en) * | 2017-03-30 | 2017-07-07 | 黑龙江大学 | A kind of method for preparing electrode of super capacitor carbon material as carbon source with radish |
CN108110260A (en) * | 2017-12-29 | 2018-06-01 | 成都新柯力化工科技有限公司 | A kind of fuel-cell catalyst and preparation method of metal-organic framework modification |
CN108963207A (en) * | 2018-06-19 | 2018-12-07 | 上海电力学院 | A kind of carbon composite material and its preparation method and application of porous metals doping |
-
2019
- 2019-03-11 CN CN201910180007.9A patent/CN109786723A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013139373A (en) * | 2011-12-28 | 2013-07-18 | Qinghua Univ | Method for producing graphene |
CN105923629A (en) * | 2016-04-26 | 2016-09-07 | 哈尔滨工程大学 | Method for preparing transition metal composite hetero atom doped porous carbon material through dipping, recrystallizing and carbonizing biomasses |
CN106927463A (en) * | 2017-03-30 | 2017-07-07 | 黑龙江大学 | A kind of method for preparing electrode of super capacitor carbon material as carbon source with radish |
CN108110260A (en) * | 2017-12-29 | 2018-06-01 | 成都新柯力化工科技有限公司 | A kind of fuel-cell catalyst and preparation method of metal-organic framework modification |
CN108963207A (en) * | 2018-06-19 | 2018-12-07 | 上海电力学院 | A kind of carbon composite material and its preparation method and application of porous metals doping |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110459772A (en) * | 2019-08-28 | 2019-11-15 | 浙江工业大学 | A kind of preparation method of the lead carbon composite for lead carbon battery cathode additive agent |
CN110459772B (en) * | 2019-08-28 | 2021-06-01 | 浙江工业大学 | Preparation method of lead-carbon composite material for lead-carbon battery cathode additive |
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