CN106997951A - It is a kind of for the negative material of sodium-ion battery and its preparation and application - Google Patents
It is a kind of for the negative material of sodium-ion battery and its preparation and application Download PDFInfo
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- CN106997951A CN106997951A CN201710339058.2A CN201710339058A CN106997951A CN 106997951 A CN106997951 A CN 106997951A CN 201710339058 A CN201710339058 A CN 201710339058A CN 106997951 A CN106997951 A CN 106997951A
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- sodium
- nickel
- ion battery
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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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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 invention provides a kind of negative material for sodium-ion battery, its chemical formula is Ni3B2O6, crystal structure is orthorhombic structure, belongs to Pnnm space groups.Present invention also offers a kind of preparation method of above-mentioned negative material for sodium-ion battery, after nickel source and boron source are well mixed, it is sintered under the conditions of oxidizing atmosphere, then through supercooling, pure phase boric acid nickel material is made in washing, baking step.The present invention has that raw material sources are wide, preparing cost, low, preparation technology flow is simple, low to the performance requirement of equipment, and product purity is high, the features such as having a safety feature.Obtained nickel borate materials application shows good storage sodium ability and excellent chemical property when sodium-ion battery.
Description
Technical field
The invention belongs to materialogy field, it is related to a kind of energy storage material, it is specifically a kind of for sodium-ion battery
Negative material and its preparation and application.
Background technology
The fast development of the environmental protection energy such as solar energy, wind energy, tide energy proposes higher for its supporting energy-storage system
Requirement and broader practice scope.As the energy-storage system for most having application prospect, the research and development of electrochmical power source is focused on
The notice of numerous scholars.Since the lithium ion battery commercialization nineties in last century, due to close with high voltage, high-energy
The advantages such as degree, memory-less effect and be rapidly developed, be widely used to now portable electric appts, electric automobile etc. side
Face；But it is due to be limited by lithium resource, people are studying the chemical cell system of alternative lithium ion battery energetically.
In the periodic table of elements, the adjacent periods of sodium element and elemental lithium in same main group, with similar physics and chemical property；This
Outside, sodium is compared with lithium, because its reserves is more rich, refines simpler, the features such as being distributed more extensive and with unique advantage.Cause
This, sodium-ion battery can be used as a kind of electrochmical power source applied to extensive energy storage.
Sodium-ion battery has similar operation principle with lithium ion battery, but is due to that sodium ion has than lithium ion more
Big ionic radius and relative difficulty carry out reversible deintercalation in electrode material, and during embedding entry/exit, easily make material knot
Structure is damaged, and makes battery capacity step-down, and cycle performance is deteriorated.Therefore the exploratory development of the electrode material of new excellent performance is sodium
The key subject of ion battery research and development.At present, such as oxo transition metal containing sodium is concentrated in the research of sodium-ion battery positive material
Compound（Such as NaxCoO2、NaxMnO2）With transition metal fluorophosphoric acid sodium salt（Such as NaVPO4F、Na2FePO4F）In terms of.And in negative pole
Research in terms of material is relatively fewer.
In research for the negative material of sodium-ion battery, in terms of Carbon Materials, because sodium ion radius is larger, it is impossible to
Reversible deintercalation is carried out in traditional graphite as anode material for lithium-ion battery, non-graphitic carbon material focuses primarily upon hard carbon and soft
Carbon.Komaba et al. improves efficiency first and stable circulation that hard carbon stores up sodium by improving the micro-structural of electrolyte and hard carbon
Property, 90% is up to using the first all coulombic efficiencies of button cell, circulation still has 220mAh/g after 100 weeks, with NaNi0.5Mn0.5O2For
The full battery that positive pole is built shows preferable cycle performance（Advanced Functional Materials. 2011, 21,
3859）.In alloy type material, Xiao etc. is prepared for SnSb/C nano-complexes using high-energy ball milling method, cyclic process first
Reversible storage sodium capacity be 544mAh/g, be demonstrated by preferable cyclical stability and high rate performance, maintained after circulating within 50 weeks
435mAh/g（Journal of the Chemical Society chemical Communications, 2012, 48,
3321）.Such material has a huge development potentiality, but its in charge and discharge process due to the volumetric expansion of electrode cause
The change of electrode material structure can cause the decay of battery capacity, so as to restrict its development.In addition, metal oxide, titanate,
Organic matter etc. can also be used as the negative material for sodium-ion battery.
With the research and development of new energy, to requirement more and more higher of the sodium-ion battery as energy storage device, people thirst for
The sodium ion negative material for the features such as working out high-energy-density, long circulation life and prepare simple.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of negative material for sodium-ion battery
And its prepare and apply, it is described this to solve prior art for the negative material of sodium-ion battery and its preparation and application
In sodium-ion battery the general technical problem of storage sodium ability.
The invention provides a kind of negative material for sodium-ion battery, its chemical formula is Ni3B2O6, crystal structure is
Orthorhombic structure, belongs to Pnnm space groups.
Present invention also offers the preparation method of the above-mentioned negative material for sodium-ion battery, nickel source and boron are weighed
Source, described nickel source any one or two kinds in nickel oxide, nickel oxalate, nickel nitrate, nickel chloride or nickel sulfate and
More than combination, described boron source in diboron trioxide, boric acid, boron nitride, ammonium borate or phenyl boric acid any one or
Two kinds of person and the combination of the above, described nickel source and the mol ratio of boron source are 3:2~3；After well mixed, in oxidizing atmosphere bar
It is sintered under part, described nickel source and boron source control heating rate to be 1 ~ 20 DEG C/min in sintering process；Sintering temperature is
500~1000℃；The sintered heat insulating time is 2-24h；Then through supercooling, wash, drying is made for the negative of sodium-ion battery
Pole material boric acid nickel material.
Further, described nickel source and boron source are from solution mixing, stirring, wet ball grinding or dry ball milling method
One or more kinds of methods mix 2 ~ 20h.
Further, described nickel source and boron source are sintered in air or oxygen.
The present invention also provides a kind of above-mentioned sodium-ion battery, and by negative pole, positive pole, electrolyte and barrier film composition, described is negative
Pole material is the above-mentioned negative material nickel borate for sodium-ion battery.
Further, above-mentioned a kind of sodium-ion battery, in 0.01V-3.0V (vs. Na+/ Na) charging/discharging voltage scope
It is interior, there are 0.9 ~ 1.2V (vs. Na+/ Na) discharge voltage plateau, with the initial reversible specific capacity more than 500mAh/g.
It is preferred that, nickel source uses nickel oxide, nickel oxalate or nickel nitrate, and boron source uses diboron trioxide, boric acid or ammonium borate；
The mol ratio of nickel source and boron source is 3:2~2.5.4 ~ 8h is mixed using dry ball milling or wet ball grinding；Then burnt in atmosphere
Knot.
As preferred technical scheme, nickel source and boron source control heating rate to be 1 ~ 20 DEG C/min in sintering process；Burn
Junction temperature is 500 ~ 1000 DEG C；The sintered heat insulating time is 2 ~ 48h；Temperature is used to be washed for 40 ~ 100 DEG C of hot water；Drying
Temperature is 40 ~ 200 DEG C, and time control is in 4 ~ 48h.More preferred, it is 2 ~ 10 DEG C/min that heating rate is controlled in sintering process；
Sintering temperature is 700 ~ 900 DEG C；The sintered heat insulating time is 3 ~ 24h；Temperature is used to be washed for 60 ~ 100 DEG C of hot water；Drying
Temperature is 60 ~ 120 DEG C, and time control is in 6 ~ 20h.
The present invention is compared with prior art, and its technological progress is significant.The boric acid nickel material of the present invention has raw material
Source is wide, preparing cost, low, preparation technology flow is simple, low to the performance requirement of equipment, and product purity is high, has a safety feature and waits spy
Point.Obtained nickel borate materials application shows good storage sodium ability and excellent chemical property when sodium-ion battery,
It is a kind of negative material for sodium-ion battery with potential using value.
Brief description of the drawings
Fig. 1 is the XRD spectrum for the boric acid nickel material that embodiment 2 is prepared；
Fig. 2 is the 1st time and the 2nd charging and discharging curve figure of the boric acid nickel material that embodiment 2 is prepared；
Fig. 3 is cycle performance figure of the boric acid nickel material for preparing of embodiment 2 under 200mA/g current densities.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Electrochemical property test：
Nickel borate negative material, conductive carbon black and the binding agent carboxymethyl cellulose that the inventive method is synthesized（CMC）By quality
Than 80:10:10 are well mixed, and are coated on copper foil, and electrode slice is struck out after drying, and 24h is dried in vacuo in 100 DEG C.
Using metallic sodium as to electrode；Mass ratio is dissolved in as 1 using 1mol/L：1 ethylene carbonate（EC）/ dimethyl carbonate
（DMC）Mixed solution in NaClO4Salting liquid is used as electrolyte；Button cell is assembled into argon gas glove box.
Electrochemical property test is carried out using the blue electricity CT2001A types cell tester in Wuhan, charging/discharging voltage scope is
0.01V~3.0V(vs. Na+/Na).Test temperature is 25 DEG C.
Embodiment 1
2.25g nickel oxide is well mixed with 1.488g boric acid by dry ball milling, in tube furnace under the conditions of air atmosphere
In 650 DEG C and constant temperature are warming up to 3 DEG C/min speed kept after 5h, naturally cool to room temperature, after 100 DEG C of hot washes,
10h drying is dried at 100 DEG C product nickel borate is made.
Embodiment 2
8.73g Nickelous nitrate hexahydrate and 1.488g boric acid is uniform by ball milling mixing, in tubular type under the conditions of air atmosphere
850 DEG C are warming up to 3 DEG C/min speed in stove and constant temperature is kept after 4h, naturally cool to room temperature, after 70 DEG C of hot washes,
12h drying is dried at 120 DEG C and obtains product nickel borate.
Fig. 1 is the XRD spectrum of boric acid nickel material, and the peak position of the XRD spectrum of material is entirely capable of and standard card（JCPDS.
No. 75-1809）On peak position and peak intensity match, the composition for illustrating obtained material is Ni3B2O6, and deposited without dephasign
.Fig. 2 is the 1st time and the 2nd charging and discharging curve figure of boric acid nickel material, as illustrated, 0.01-3.0V charging/discharging voltage model
In enclosing, in first time discharge process, there is an obvious discharge platform, and identical do not occur in second of discharge process
Platform, illustrates that structure evolution occurs during first charge-discharge in material.In charging process twice, two charging curve shape phases
Seemingly, there is not obvious charging voltage platform.Fig. 3 is circulation of the boric acid nickel material under 200mA/g charging and discharging currents density
Performance map, as illustrated, the 2nd discharge capacity is 494.7mA/g, the capacity of nickel borate is still kept after 60 circulations
292.8mAh/g, illustrates that inventing the material has certain cycle performance and chemical property.
Embodiment 3
4.41g nickel oxalate and 1.488g boric acid is uniform by ball milling mixing, with 5 DEG C/min speed under the conditions of air atmosphere
It is warming up to after 750 DEG C and constant temperature 10h, naturally cools to room temperature, after 80 DEG C of hot washes, 8h is dried at 100 DEG C
To product nickel borate.
Embodiment 4
The boric acid of 7.89g nickel sulfate and 1.488g is uniformly mixed by solution, 8h is dried under the conditions of 90 DEG C and is made
Presoma.Presoma is warming up to 900 DEG C under the conditions of air atmosphere with 8 DEG C/min speed and constant temperature is kept after 15h, naturally cools to
Room temperature, after 80 DEG C of hot wash, 9h drying is dried at 110 DEG C and obtains product nickel borate.
Embodiment 5
8.73g nickel nitrate and 0.72g diboron trioxide is uniform by ball milling mixing, under the conditions of air atmosphere with 5 DEG C/
Min speed is warming up to after 900 DEG C and constant temperature 10h, naturally cools to room temperature, after 90 DEG C of hot washes, 15h is dried at 80 DEG C
Drying obtains product nickel borate.
Embodiment 6
4.41g nickel oxalate is well mixed with 0.72g diboron trioxide by wet ball grinding, with 5 under the conditions of air atmosphere
DEG C/min speed is warming up to after 700 DEG C and constant temperature 8h, room temperature is naturally cooled to, after 90 DEG C of hot washes, is dried at 120 DEG C
8h drying obtains product nickel borate.
Embodiment 7
7.89g nickel sulfate and 0.72g diboron trioxide is uniform by ball milling mixing, under the conditions of air atmosphere with 3 DEG C/
Min speed is warming up to after 850 DEG C and constant temperature 15h, naturally cools to room temperature, after 80 DEG C of hot washes, is dried at 100 DEG C
10h obtains product nickel borate.
Embodiment 8
It is 3 that the mixture of nickel oxide, the mixture of nickel nitrate and ammonium borate and phenyl boric acid is pressed into nickel boron mol ratio:2.2 dry method balls
4h is to uniform for mill mixing, is sintered under air conditionses, and it is 3 DEG C/min, sintering temperature that heating rate is controlled in sintering process
For 800 DEG C, the sintered heat insulating time is 12h, uses temperature to be washed for 60 DEG C of hot water after cooling；The drying temperature is controlled to be again
60 DEG C, drying and processing 20h prepares boric acid nickel material.
Embodiment 9
It is 3 in molar ratio by nickel nitrate and boron nitride:2.2 wet ball grinding mixing 20h are burnt to uniform under Oxygen Condition
It is 10 DEG C/min that heating rate is controlled in knot, sintering process, and sintering temperature is 900 DEG C, and the sintered heat insulating time is 3h, is adopted after cooling
Washed with 100 DEG C of hot water；It is 150 DEG C to control drying temperature again, and drying and processing 4h prepares boric acid nickel material.
Above said content is only the basic explanation under present inventive concept, and according to appointing that technical scheme is done
What equivalent transformation, all should belong to protection scope of the present invention.
Claims (6)
1. a kind of negative material for sodium-ion battery, it is characterised in that：Its chemical formula is Ni3B2O6, crystal structure is orthogonal
Crystal structure, belongs to Pnnm space groups.
2. a kind of preparation method of negative material for sodium-ion battery described in claim 1, it is characterised in that:Weigh nickel
Source and boron source, described nickel source in nickel oxide, nickel oxalate, nickel nitrate, nickel chloride or nickel sulfate any one or
Two kinds and the combination of the above, described boron source are any in diboron trioxide, boric acid, boron nitride, ammonium borate or phenyl boric acid
The combination of one or two kinds of and the above, described nickel source and the mol ratio of boron source are 3:2~3；After well mixed, in oxidisability
It is sintered under atmospheric condition, described nickel source and boron source control heating rate to be 1 ~ 20 DEG C/min in sintering process；Sintering
Temperature is 500 ~ 1000 DEG C；The sintered heat insulating time is 2-24h；Then through supercooling, wash, drying, be made for sodium ion electricity
The negative material boric acid nickel material in pond.
3. a kind of preparation method of negative material for sodium-ion battery according to claim 2, it is characterised in that：Institute
One or more kinds of methods mixing 2 of the nickel source and boron source stated from solution mixing, stirring, wet ball grinding or dry ball milling method
~20h。
4. a kind of preparation method of negative material for sodium-ion battery according to claim 2, it is characterised in that：Institute
The nickel source and boron source stated are sintered in air or oxygen.
5. a kind of sodium-ion battery, it is characterised in that：By negative pole, positive pole, electrolyte and barrier film composition, described negative material is
A kind of negative material for sodium-ion battery described in claim 1.
6. a kind of sodium-ion battery according to claim 1, it is characterised in that：In 0.01V-3.0V charging/discharging voltage scopes
It is interior, there is 0.9 ~ 1.2V discharge voltage plateau, with the initial reversible specific capacity more than 500mAh/g.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107681141A (en) * | 2017-09-26 | 2018-02-09 | 福建师范大学 | A kind of anode material of lithium-ion battery of carbon coating boric acid nanosized nickel rods |
| CN109279663A (en) * | 2018-11-09 | 2019-01-29 | 上海电力学院 | A kind of borate family anode material of lithium-ion battery and its preparation and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105702956A (en) * | 2015-12-28 | 2016-06-22 | 上海电力学院 | Negative material for sodium-ion battery and preparation method of negative material |
| CN107086300A (en) * | 2017-04-20 | 2017-08-22 | 上海电力学院 | It is a kind of for the negative material of sodium-ion battery and its preparation and application |
-
2017
- 2017-05-15 CN CN201710339058.2A patent/CN106997951A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105702956A (en) * | 2015-12-28 | 2016-06-22 | 上海电力学院 | Negative material for sodium-ion battery and preparation method of negative material |
| CN107086300A (en) * | 2017-04-20 | 2017-08-22 | 上海电力学院 | It is a kind of for the negative material of sodium-ion battery and its preparation and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107681141A (en) * | 2017-09-26 | 2018-02-09 | 福建师范大学 | A kind of anode material of lithium-ion battery of carbon coating boric acid nanosized nickel rods |
| CN109279663A (en) * | 2018-11-09 | 2019-01-29 | 上海电力学院 | A kind of borate family anode material of lithium-ion battery and its preparation and application |
| CN109279663B (en) * | 2018-11-09 | 2021-05-04 | 上海电力学院 | Borate sodium-ion battery negative electrode material and preparation and application thereof |
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