CN109301178A - A kind of sodium Dual-ion cell of the novel carbon negative pole material preparation of doping phosphorus - Google Patents
A kind of sodium Dual-ion cell of the novel carbon negative pole material preparation of doping phosphorus Download PDFInfo
- Publication number
- CN109301178A CN109301178A CN201810938368.0A CN201810938368A CN109301178A CN 109301178 A CN109301178 A CN 109301178A CN 201810938368 A CN201810938368 A CN 201810938368A CN 109301178 A CN109301178 A CN 109301178A
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- Prior art keywords
- phosphorus
- sodium
- carbon
- doping
- negative pole
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 invention discloses a kind of sodium Dual-ion cells of the novel carbon negative pole material preparation of doping phosphorus, the novel carbon negative pole material of the doping phosphorus is mixed with by carbon material and phosphorus, the carbon material content is 30-90%, the phosphorus content is 10-70%, the sodium Dual-ion cell includes carbon positive electrode, electrolyte and the doping novel carbon negative pole material of phosphorus, and the electrolyte is the sodium salt electrolyte of 0.1-5M.The doping of phosphate material in negative electrode material of the present invention, because the interlamellar spacing of phosphorus reaches 0.53nm, bigger than the interlamellar spacing of graphite is more, it is more advantageous to the insertion of battery charging process sodium ion, increase considerably the load capacity of sodium ion in negative electrode material, so as to significantly promote battery capacity, it is remarkably enhanced using the New Type of Carbon of doping phosphorus as the specific capacity of the sodium Dual-ion cell of negative electrode material.
Description
Technical field
The present invention relates to sodium-ion battery, Dual-ion cell technical field more particularly to a kind of novel Carbon anodes of doping phosphorus
The sodium Dual-ion cell of material preparation.
Background technique
Lithium ion battery (LIBs) is due to its relatively high discharge voltage, energy density and good power-performance, institute
It is applied to portable electronic product and network storage with ubiquitous.With modern science and technology progress and demand, high-energy is developed
Density, the Novel rechargeable battery system of low cost are receive more and more attention.At present market-oriented lithium from
Sub- battery generally uses cobalt acid lithium, LiMn2O4, LiFePO4 and ternary material etc. as positive electrode, these material prices are high
It is expensive, so that lithium ion battery higher cost.Furthermore due to organic electrolysis plastidome etc., the internal resistance of cell is relatively large, cannot
Heavy-current discharge.
Dual-ion cell (DIBs) has had been found to several as the electrical energy storage device of a kind of high-energy and low cost
10 years.Dual-ion cell generally uses graphite as the negative electrode material of sodium Dual-ion cell at present, but sodium ion diameter is much larger than
The interlamellar spacing (0.24nm) of graphite, therefore graphite cathode is not easy to be embedded in limited amount, battery capacity is not by the insertion of sodium ion
Height, performance are not able to satisfy industrialized requirement.Therefore to promote sodium-ion battery performance, seek the cathode of more conducively sodium ion insertion
Material seems most important.
Summary of the invention
For solve at high cost, sodium ion size existing for current lithium ion battery it is larger be not easy to be embedded in graphite cathode material with
And the problems such as commercialization is also not implemented in sodium Dual-ion cell, the present invention provides a kind of novel carbon negative pole material preparations of doping phosphorus
Sodium Dual-ion cell.
In order to solve the above technical problems, the technical scheme adopted by the invention is that: a kind of novel carbon negative pole material of doping phosphorus
The sodium Dual-ion cell of preparation, the novel carbon negative pole material of the doping phosphorus are mixed with by carbon material and phosphorus, the carbon materials
Material content is 30-90%, and the phosphorus content is 10-70%, and the sodium Dual-ion cell includes carbon positive electrode, electrolyte and mixes
The miscellaneous novel carbon negative pole material of phosphorus, the electrolyte are the sodium salt electrolyte of 0.1-5M.
Further, the preparation step of the doping novel carbon negative pole material of phosphorus is to mix carbon material and phosphorus ratio, so
The grinding of 4-12h is carried out afterwards, so that carbon material and the full and uniform mixing of phosphorus, then by carbon and phosphorus mixing material in high temperature anoxybiotic environment
Under be heated to 380-430 DEG C, be rapidly cooled to room temperature after keeping the temperature 2-5h.
Further, the carbon material is at least one of graphene, carbon nanotube etc..
Further, the phosphorus is one of red phosphorus, white phosphorus.
Further, the positive carbon material is graphene, graphite, graphite powder, nano-graphite, soft carbon, hard carbon, natural stone
At least one of ink, electrographite, carbon nanotube, expanded graphite, coated graphite, three-dimensional grapheme etc..
Further, the electrolyte of the sodium salt electrolyte is sodium fluoride (NaF), sodium hexafluoro phosphate (NaPF6), tetrafluoro boron
At least one of sour sodium (NaBF4), sodium perchlorate (NaClO4) etc..
Further, the solvent of the sodium salt electrolyte is ethylene carbonate (EC), propene carbonate (PC), carbonic acid diformazan
Ester (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), fluorinated ethylene carbonate (FEC),
1,3- dioxy ring, penta ring (DOL), 1,2- dimethoxy-ethane (DME), butylene (BC), methyl esters (PA), methyl acetate
At least one of (MA) etc..
By the above-mentioned description to structure of the invention it is found that compared to the prior art, the present invention has the advantage that
(1) in negative electrode material of the present invention phosphate material doping because the interlamellar spacing of phosphorus reaches 0.53nm, than the interlayer of graphite
Away from big more, it is more advantageous to the insertion of battery charging process sodium ion, increases considerably the load capacity of sodium ion in negative electrode material,
So as to significantly promote battery capacity.
(2) new carbon provided by the invention using doping phosphorus has such as the sodium Dual-ion cell of negative electrode material
Lower characteristic: in 100mA g-1Current density under charge and discharge cycles, initial charge capacity and discharge capacity respectively reach
697.2mAh g-1With 657.3mAh g-1, coulombic efficiency reaches 94.28% for the first time, the discharge capacity of second of charge and discharge cycles
Still reach 605.4mAh g-1.The ratio for the sodium Dual-ion cell for using the New Type of Carbon of doping phosphorus as negative electrode material is absolutely proved
Capacity is remarkably enhanced.
Detailed description of the invention
The attached drawing constituted part of this application is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the sodium Dual-ion cell of the embodiment of the present invention 1 in 100mA g-1The charge and discharge cycles curve graph of current density；
Fig. 2 is the sodium Dual-ion cell of the embodiment of the present invention 2 in 100mA g-1The charge and discharge cycles curve graph of current density.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
A kind of sodium Dual-ion cell of doping phosphorus novel carbon negative pole material preparation, the novel carbon negative pole material of the doping phosphorus by
Carbon material and phosphorus are mixed with, and the carbon material content is 30-90%, and the phosphorus content is 10-70%, the sodium it is double from
The carbon containing positive electrode of sub- battery pack, electrolyte and the doping novel carbon negative pole material of phosphorus, the sodium salt electricity that the electrolyte is 0.1-5M
Solve liquid.
The preparation step of the doping novel carbon negative pole material of phosphorus is to mix carbon material and phosphorus ratio, then carries out 4-
The grinding of 12h, so that carbon material and the full and uniform mixing of phosphorus, then carbon and phosphorus mixing material are heated under high temperature anoxybiotic environment
It 380-430 DEG C, being rapidly cooled to room temperature after keeping the temperature 2-5h, the carbon material is at least one of graphene, carbon nanotube etc.,
The phosphorus is one of red phosphorus, white phosphorus.
The anode carbon material is graphene, graphite, graphite powder, nano-graphite, soft carbon, hard carbon, natural graphite, artificial stone
At least one of ink, carbon nanotube, expanded graphite, coated graphite, three-dimensional grapheme etc..
The electrolyte of the sodium salt electrolyte is sodium fluoride (NaF), sodium hexafluoro phosphate (NaPF6), sodium tetrafluoroborate
(NaBF4), at least one of sodium perchlorate (NaClO4) etc., the solvent of the sodium salt electrolyte be ethylene carbonate (EC),
Propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate
(MPC), fluorinated ethylene carbonate (FEC), 1,3- dioxy ring, penta ring (DOL), 1,2- dimethoxy-ethane (DME), butylene carbonate
At least one of ester (BC), methyl esters (PA), methyl acetate (MA) etc..
Embodiment 1
Adulterate sodium Dual-ion cell of the carbon material of red phosphorus as negative electrode material
The sodium Dual-ion cell of the present embodiment is using the carbon material of doping red phosphorus as negative electrode material, and wherein red phosphorus accounts for cathode
The 30% of material gross mass, carbon material are graphene, account for the 70% of negative electrode material gross mass；Negative electrode material preparation process is will
70% graphene and 30% red phosphorus uniformly mix, and then grind 10h, obtain novel carbon negative pole material.Using nano-graphite
As positive electrode；1M lithium hexafluoro phosphate (LiPF6) volume ratio is dissolved in for diethyl carbonate (DEC): dimethyl carbonate (DMC)=
The mixed solution of 7:3 (v1:v2=7:3) is as electrolyte；And carry out the assembling of sodium Dual-ion cell and performance test.
As shown in Figure 1, having studied the chemical property of the present embodiment lithium Dual-ion cell using charging and discharging curve.From figure
It can be seen that sodium Dual-ion cell is in 100mA g-1Charge and discharge cycles under current density, initial charge capacity and discharge capacity point
Do not reach 697.2mAh g-1With 657.3mAh g-1, coulombic efficiency reaches 94.28% for the first time, and second charge and discharge cycles are put
Capacitance still reaches 605.4mAh g-1.The sodium double ion using the New Type of Carbon of doping red phosphorus as negative electrode material is absolutely proved
The specific capacity of battery is remarkably enhanced.
Embodiment 2
Adulterate sodium Dual-ion cell of the carbon material of white phosphorus as negative electrode material
The sodium Dual-ion cell of the present embodiment is using the carbon material of doping white phosphorus as negative electrode material, and wherein white phosphorus accounts for cathode
The 45% of material gross mass, carbon material are nano-graphite, account for the 55% of negative electrode material gross mass；Negative electrode material preparation process is will
55% graphene and 45% white phosphorus uniformly mix, and then grind 10h, then by carbon and phosphorus mixing material in high temperature anoxybiotic ring
It is heated to 400 DEG C under border, is rapidly cooled to room temperature to obtain novel carbon negative pole material after keeping the temperature 5h.Using graphene as positive material
Material；2M lithium hexafluoro phosphate (LiPF6) volume ratio is dissolved in for diethyl carbonate (DEC): methyl ethyl carbonate (EMC)=6:4 (v1:v2
=6:4) mixed solution as electrolyte；And carry out the assembling of sodium Dual-ion cell and performance test.
As shown in Fig. 2, having studied the chemical property of the present embodiment lithium Dual-ion cell using charging and discharging curve.From figure
It can be seen that sodium Dual-ion cell is in 100mA g-1Charge and discharge cycles under current density, initial charge capacity and discharge capacity point
Do not reach 615.8mAh g-1With 586.5mAh g-1, coulombic efficiency reaches 95.24% for the first time, and second charge and discharge cycles are put
Capacitance still reaches 541.24mAh g-1.The sodium double ion using the New Type of Carbon of doping white phosphorus as negative electrode material is absolutely proved
The specific capacity of battery is remarkably enhanced.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (7)
1. a kind of sodium Dual-ion cell of the novel carbon negative pole material preparation of doping phosphorus, it is characterised in that: the doping phosphorus New Type of Carbon
Negative electrode material is mixed with by carbon material and phosphorus, and the carbon material content is 30-90%, and the phosphorus content is 10-70%,
The sodium Dual-ion cell includes carbon positive electrode, electrolyte and the doping novel carbon negative pole material of phosphorus, and the electrolyte is 0.1-
The sodium salt electrolyte of 5M.
2. the sodium Dual-ion cell of the novel carbon negative pole material preparation of a kind of doping phosphorus according to claim 1, it is characterised in that:
The preparation step of the doping novel carbon negative pole material of phosphorus is to mix carbon material and phosphorus ratio, then carries out the grinding of 4-12h,
So that carbon material and the full and uniform mixing of phosphorus, then carbon and phosphorus mixing material are heated to 380-430 DEG C under high temperature anoxybiotic environment,
It is rapidly cooled to room temperature after heat preservation 2-5h.
3. the sodium Dual-ion cell of the novel carbon negative pole material preparation of a kind of doping phosphorus according to claim 1, it is characterised in that:
The carbon material is at least one of graphene, carbon nanotube etc..
4. the sodium Dual-ion cell of the novel carbon negative pole material preparation of a kind of doping phosphorus according to claim 1, it is characterised in that:
The phosphorus is one of red phosphorus, white phosphorus.
5. the sodium Dual-ion cell of the novel carbon negative pole material preparation of a kind of doping phosphorus according to claim 1, it is characterised in that:
The anode carbon material is graphene, graphite, graphite powder, nano-graphite, soft carbon, hard carbon, natural graphite, electrographite, carbon are received
At least one of mitron, expanded graphite, coated graphite, three-dimensional grapheme etc..
6. the sodium Dual-ion cell of the novel carbon negative pole material preparation of a kind of doping phosphorus according to claim 1, it is characterised in that:
The electrolyte of the sodium salt electrolyte is sodium fluoride (NaF), sodium hexafluoro phosphate (NaPF6), sodium tetrafluoroborate (NaBF4), perchloric acid
Sodium (NaClO4At least one of) etc..
7. the sodium Dual-ion cell of the novel carbon negative pole material preparation of a kind of doping phosphorus according to claim 1, it is characterised in that:
The solvent of the sodium salt electrolyte is ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), carbonic acid diethyl
Ester (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), fluorinated ethylene carbonate (FEC), 1,3- dioxy ring, penta ring
(DOL), 1,2- dimethoxy-ethane (DME), at least one in butylene (BC), methyl esters (PA), methyl acetate (MA) etc.
Kind.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110265722A (en) * | 2019-06-14 | 2019-09-20 | 中国科学院长春应用化学研究所 | A kind of Dual-ion cell electrolyte and application |
| CN110600736A (en) * | 2019-08-22 | 2019-12-20 | 深圳先进技术研究院 | Non-metal ion secondary battery and preparation method thereof |
| CN113113601A (en) * | 2021-04-06 | 2021-07-13 | 常德速碳新能源科技有限公司 | Hard carbon negative electrode material for lithium ion secondary battery and preparation method thereof |
| CN113725425A (en) * | 2021-08-27 | 2021-11-30 | 昆明理工大学 | High-safety and high-performance battery negative electrode material |
| CN113745011A (en) * | 2021-08-31 | 2021-12-03 | 西安交通大学 | Application of red phosphorus/carbon nanotube composite material in sodium ion capacitor |
| CN114784251A (en) * | 2022-05-13 | 2022-07-22 | 中国科学技术大学 | Phosphorus-coated negative electrode material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113745011A (en) * | 2021-08-31 | 2021-12-03 | 西安交通大学 | Application of red phosphorus/carbon nanotube composite material in sodium ion capacitor |
| CN114784251A (en) * | 2022-05-13 | 2022-07-22 | 中国科学技术大学 | Phosphorus-coated negative electrode material and preparation method and application thereof |
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