CN110277557A - The preparation method and storage sodium performance of the biological carbon material of multi-element doping, high-specific surface area, threadiness - Google Patents
The preparation method and storage sodium performance of the biological carbon material of multi-element doping, high-specific surface area, threadiness Download PDFInfo
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- CN110277557A CN110277557A CN201810221146.7A CN201810221146A CN110277557A CN 110277557 A CN110277557 A CN 110277557A CN 201810221146 A CN201810221146 A CN 201810221146A CN 110277557 A CN110277557 A CN 110277557A
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- carbon material
- surface area
- specific surface
- threadiness
- element doping
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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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- 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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- 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 methods that sodium ion battery electrode material is prepared as presoma using the marine organism material of charing.Its maximum feature is only by simply pre- carbonization and carbonization treatment, and does not obtain the threadiness biology carbon electrode material of multi-element doping plus under conditions of activator.The preparation method is by pretreated shark bone in N2Atmosphere under, first in the pre- carbonization treatments of 500 DEG C of calcining 2h progress, then again in 900 DEG C of charing 2h.Products therefrom carries out pickling, and is washed with deionized water to neutrality, is made after drying.Biological carbon material prepared by this method has the characteristics that multi-element doping, high-specific surface area, fibrous structure, has advantage that is at low cost, simple, being easy to produce in enormous quantities in method.Meanwhile the material shows excellent chemical property as sodium ion battery electrode material.
Description
Technical field
The invention belongs to chemical energy source Material Field, provides a kind of high temperature cabonization and prepare multi-element doping, high-ratio surface
The method of the biological carbon material of product, threadiness, outstanding feature are not activated and obtain N, P, S, O multi-element doping, high ratio
The biological carbon material of surface area, threadiness, can be used as the use of sodium-ion battery cathode.
Background technique
Lithium ion battery have the advantages that high-energy density, long circulation life and in portable electronic device and new energy vapour
Vehicle field occupies an important position.However, the reserves of lithium are limited on the earth, it is unevenly distributed.With new energy field and electronic vapour
The ecology potential of the rapid development of garage's industry, lithium ion battery must be by the serious restriction of lithium resource shortage.Therefore, research and development provides
Extensive, the cheap secondary cell instead of lithium ion battery in source becomes domestic to meet the energy storage demand of rapid growth
The hot spot of outer research.
There is the metallic sodium of similar physico-chemical performance with lithium, rich reserves are widely distributed, and cheap, therefore close
The exploitation of year sodium-ion battery in terms of energy storage attracts attention.One of main electrode material as current sodium-ion battery, carbon
The advantages that material is due to specific surface area with higher, regulatable pore structure, excellent electric conductivity, environmental-friendly and inexpensive
It receives significant attention.In order to promote the performance of carbon material, the approach of chemical activation and Heteroatom doping is generallyd use.Its method
Are as follows: the sample and activator that need to be handled (specifically include that KOH, NaOH, K2CO3, Na2CO3, KHCO3, NaHCO3Deng) mixed
It closes, under inert gas protection reheating, handles certain time, gained sample is cleaned multiple times to obtain porous carbon structure into mistake.
Carbon material through overactivation, although increasing aperture quantity and having widened pore-size distribution, activation destroys presoma pattern
Than more serious, the carbon material after activation loses the pattern of script substantially, and pattern is single, substantially lamellar structure；Secondly, living
Change processing needs reheating, and requires heat to higher temperature, and needs to mix various chemistry during activating
Activator is likely to result in pollution to environment.Another method is increased between carbon-coating by adulterating hetero atom in carbon base body
Away from improving insertion of the sodium ion in carbon material and move out, can effectively promote the storage sodium performance of carbon material.But doping process
Doping reagent need to be additionally introduced, and carries out high-temperature process, increases cost.
Currently, using cheap biomass waste resource as presoma, using pyrolysis carbonization technology prepare carbon material at
For a kind of very promising method.Biomass constructs diversified biological structure in 1 years evolutionary process, thus
Good template is provided for the preparation of porous carbon materials；Meanwhile biomass often contains multiple element ingredient, these hetero atoms
Carbon base body is directly entered during high temperature cabonization, it can be achieved that in situ doping of the hetero atom in carbon base body.Therefore, this patent selects
It selects shark bone and is prepared for N, P, S, O multielement, high-specific surface area, fibrous carbon material, table by being directly pyrolyzed for presoma
Reveal excellent chemical property.
Summary of the invention
The technical problem to be solved by the present invention is to be prepared with simple method by the unique ingredient of biomass and structure
Carbon material, and make it have preferable storage sodium performance.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
Appropriate pretreated shark bone is taken, is put into porcelain boat, in N2Atmosphere in carry out continuous warming, presoma is subjected to carbon
Change, obtains carbon material sample after cooling.Sample dilute hydrochloric acid and/or deionized water are cleaned into removal impurity, are in neutrality to solution
When, the fibrous carbon material of high-specific surface area, multi-element doping is obtained after dry.
Compared with prior art, the beneficial effects of the present invention are embodied in:
(1) marine biomass --- shark bone as presoma, have easily obtain, renewable is strong, the excellent honest and clean spy of price
Point；
(2) during obtaining electrode material, it is not added with any activator, obtains high-specific surface area, polynary only by heating
The fibrous carbon material of element doping.This simple synthetic route production cost is low, environmental-friendly pollution-free, can carry out large quantities of
The production of amount；
(3) when the electrode material obtained is applied to sodium-ion battery electrode, excellent chemical property is shown as.
Detailed description of the invention
Fig. 1 is multi-element doping, high-specific surface area, fibrous carbon scanning of materials Electronic Speculum (SEM) photograph that embodiment 1 obtains
Piece.
Fig. 2 be embodiment 1 obtain multi-element doping, high-specific surface area, fibrous carbon material nitrogen adsorption-desorption
Curve.
Fig. 3 be embodiment 1 obtain multi-element doping, high-specific surface area, fibrous carbon material pore size distribution curve.
Fig. 4 be embodiment 1 obtain multi-element doping, high-specific surface area, fibrous carbon material x-ray photoelectron energy
Spectrum analysis (XPS) curve.
Fig. 5 be embodiment 1 obtain multi-element doping, high-specific surface area, fibrous carbon material in application examples 1, with
0.2Ag-1Current density charging and discharging curve.
Fig. 6 be embodiment 1 obtain multi-element doping, high-specific surface area, fibrous carbon material in application examples, respectively
With 0.2Ag-1、0.5Ag-1、1Ag-1、2Ag-1、5Ag-1、10Ag-1Current density charging and discharging curve.
Fig. 7 be embodiment 1 obtain multi-element doping, high-specific surface area, fibrous carbon material in application examples 2, with
0.2Ag-1Current density charging and discharging curve.
Specific embodiment
It explains referring now to following specific embodiments to the present invention, but is not limited only to embodiment.
Embodiment 1
The shark bone bought boils 1h in the NaOH for the 1M for being heated to 90 DEG C, until the meat of shark bone surface is detached from, obtains brilliant white
Smooth shark bone.This shark bone is cleaned, baking oven drying is placed, obtains presoma.The presoma of drying is put into magnetic boat,
With 2 DEG C of min under nitrogen atmosphere-1Speed be warming up to 500 DEG C, and keep the temperature 2h at this temperature, then proceed to be warming up to 900 DEG C,
Keep the temperature 2h.Product is taken out after natural cooling.Product is cleaned for 24 hours with the hydrochloric acid of 3M at room temperature, then abundant with deionized water
Cleaning removal impurity, is dried to obtain more doping, high-specific surface area, fibrous carbon materials at 80 DEG C.
Application examples 1
Obtained sample, conductive agent Super P, binder (sodium carboxymethylcellulose, CMC) are mixed with the mass ratio of 8:1:1
Afterwards, water is added to be fully ground, and uniformly drips to and electrode slice is made on copper sheet.This experiment is by assembling the button-shaped sodium of CR2032 type
Ion battery battery is tested for the property, in the glove box full of Ar gas, electrode slice, diaphragm, lithium piece, gasket and spring
This five kinds of articles of piece are encapsulated in battery case in certain sequence, and 1mol/L NaClO is added dropwise4EC/DEC solution as electrolyte.
Constant current charge-discharge curve is then tested on blue electrical measurement test system (CT2001A), test result such as Fig. 5, Fig. 6.
From fig. 5, it can be seen that in 0.2Ag-1Constant current charge-discharge test in, the present invention prepared by multi-element doping, height
Specific surface area, fibrous carbon material pass through the implementation of the process, and embedding sodium capacity is 3140.5mAh g to product for the first time-1, reversible removing sodium
Capacity 707mAhg-1, second is respectively 665.1mAhg with the discharge capacity after the tenth circulation-1And 637.5mAhg-1, performance
For especially excellent storage sodium performance.
From fig. 6, it can be seen that in 0.2Ag-1、0.5Ag-1、1Ag-1、2Ag-1、5Ag-1、10Ag-1It is filled under different current densities
Electric discharge, specific discharge capacity is respectively 601mAhg-1, 446mAhg-1, 365.4mAhg-1, 282mAhg-1, 212.6mAhg-1,
150.1mAhg-1, show excellent storage sodium performance.
Application examples 2
This application case is identical as application examples 1, difference are as follows: electrolyte is by 1mol/L NaClO4EC/DEC solution be exchanged with
1mol/L NaCFSO3DIGLYME solution.Shown in Fig. 7, in 0.2Ag-1Constant current charge-discharge test in, the present invention prepared by
More doping, high-specific surface area, fibrous carbon material are by the implementation of the process, and embedding sodium capacity is 964.2mAh g to product for the first time-1,
Reversible removing sodium capacity 748.3mAhg-1, second is respectively 679.3mAhg with the discharge capacity after the tenth circulation-1With
651.4mAhg-1, compared with application examples 2, after using electrolyte instead, first circle coulombic efficiency is promoted by 22.51% to 77.6%, is being kept
Simultaneously, first circle coulombic efficiency is promoted extra high specific discharge capacity suddenly.
Claims (6)
1. a kind of method for preparing the biological carbon material of multi-element doping, high-specific surface area, threadiness using shark bone, feature exist
In including following step:
(a) raw material selected by is the ocean class fish-bone based on shark bone；
(b) pre-process: shark bone at room temperature for a period of time, for removing the pulp adhered on shark bone, dry by alkali cleaning
The smooth shark bone presoma of brilliant white is obtained afterwards；
(c) carbonization and carbonization in advance: the presoma after drying is put into tube furnace, under an inert atmosphere with certain heating
Rate is warming up to suitable pre- carburizing temperature, and held for some time, then raises temperature to carbonization temperature and is carbonized；
(d) it cleans: calcined sample is cleaned, sufficiently cleaning removes impurity in dilute hydrochloric acid, deionized water respectively,
After solution is washed till neutrality, dry in an oven.
2. the preparation method of the biological carbon material of multi-element doping according to claim 1, high-specific surface area, threadiness,
It is characterized in that: in stepb, using marine biomass-shark bone as presoma, being not added with any activator.
3. the preparation method of the biological carbon material of multi-element doping according to claim 1, high-specific surface area, threadiness,
It is characterized in that: in step c, in N2Atmosphere under, pre- carburizing temperature be 500 DEG C, carbonization temperature be 800 ~ 1100 DEG C, heating speed
Rate is 2 DEG C of min-1, soaking time 2h.
4. the preparation method of the biological carbon material of multi-element doping according to claim 1, high-specific surface area, threadiness,
Be characterized in that: in step d, sample cleans 24-48h with 3M hydrochloric acid at room temperature after cooling.
5. the preparation method of the biological carbon material of -4 multi-element dopings, high-specific surface area, threadiness according to claim 1,
It is characterized in that any activator is not used, obtains a kind of multi-element doping, high-specific surface area, threadiness biology only by calcining
Carbon material.
6. the preparation method of the biological carbon material of multi-element doping described in -5, high-specific surface area, threadiness according to claim 1,
It is characterized by: the fibrous carbon material can be applied to the negative electrode material of sodium-ion battery, and show as excellent storage sodium performance.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111591973A (en) * | 2020-06-29 | 2020-08-28 | 盐城工学院 | Suaeda salsa-based porous carbon and preparation method thereof |
| CN112687877A (en) * | 2020-12-24 | 2021-04-20 | 李树成 | Preparation method of super-high-magnification negative electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111591973A (en) * | 2020-06-29 | 2020-08-28 | 盐城工学院 | Suaeda salsa-based porous carbon and preparation method thereof |
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| CN112687877A (en) * | 2020-12-24 | 2021-04-20 | 李树成 | Preparation method of super-high-magnification negative electrode material |
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Application publication date: 20190924 |