CN108054443A - Water system sodium ion secondary battery - Google Patents
Water system sodium ion secondary battery Download PDFInfo
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- CN108054443A CN108054443A CN201711347820.8A CN201711347820A CN108054443A CN 108054443 A CN108054443 A CN 108054443A CN 201711347820 A CN201711347820 A CN 201711347820A CN 108054443 A CN108054443 A CN 108054443A
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- Prior art keywords
- water system
- ion secondary
- secondary battery
- sodium
- sodium ion
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of water system sodium ion secondary batteries.The battery includes anode, cathode, membrane and electrolyte, and the active material of anode is Prussian Zn3[Fe(CN)6]2, the active material of cathode is titanium phosphate sodium, and the solute of electrolyte is sodium perchlorate and polyethylene glycol.The present invention is in aqueous electrolyte, by adding in polyethylene glycol, has not only maintained the advantages of aqueous electrolyte intermediate ion mobility is high, but also drastically increases the operating voltage window of electrolyte stabilization, while improves the stability of electrode material.The water system sodium ion secondary battery of the present invention has the chemical property of high voltage, high magnification and high stability, charge-discharge performance test is carried out under the electric current of 1C=60mA/g, operating voltage is 1.6V~1.65V, multiplying power can reach more than 40C and period hundred times, for its coulombic efficiency close to 100%, capacity retention ratio is more than 90%.
Description
Technical field
The invention belongs to battery technology fields, are related to a kind of water system sodium ion secondary battery.
Background technology
Water system ion battery is concerned due to its is safer and is expected to and realizes fast charging and discharging.Its operation principle and two
Secondary lithium ion battery is similar, and compared with present organic secondary ion battery, water system ion battery has low cost, high safety
Property, the advantages such as environmental-friendly and ionic mobility is high.
Lithium rechargeable battery is widely used because of its higher energy density and longer service life, especially
In the high-tech electronics product such as laptop, mobile phone, camera, the small light of electronic equipment has been promoted.But because
Using organic solution as electrolyte, so that the migration rate of ion limits the fast of battery well below aqueous electrolyte
Fast charge and discharge.In addition, organic electrolyte is generally all toxic, and easily burning at a higher temperature, this gives environment and people
Body all brings larger security risk.According to different ionic species, water system ion secondary battery can be divided into alkali metal ion
Battery (Li+、Na+And K+Deng) and high volence metal ion battery (Mg2+、Zn2+And Al3+Deng).It is active due to high volence metal ion
Property and the reasons such as charge density, cause its insertion and abjection in electrode material all more difficult, it is difficult to find suitable electricity
Pole material.Therefore, current research is mainly on water-system alkali metal ion battery.Compared with aquo-lithium ion battery, water system
Sodium-ion battery is expected to reduce cost due to its abundant sodium resource (crustal abundance 2.74%), for extensive, fixed storage
Energy occasion, water system sodium-ion battery are considered as the ideal chose for substituting aquo-lithium ion battery as next-generation accumulation power supply.
The water system sodium-ion battery being currently known mainly has NaMn2(CN)6/Na2CuFe(CN)6(M.Pasta,et
al.Commun.2014,5,3007)、K0.27MnO2/NaTi2(PO4)3(L.Yang,et al,Acs
Appl.Mater.Interfaces.2016,8,14564-14571), Na3MnTi(PO4)3/Na3MnTi(PO4)3(H.Gao,
J.B.Goodenough, Angew.Chem.Int.Ed.2016,55,12768-12772) and PPy/KCuFe (CN)6
(M.Pasta, et al.Commun.2012,3,1149) etc..But they all there is operating voltage low (＜ 1.5V) and service life
The problem of short.
The content of the invention
The object of the present invention is to provide a kind of operating voltage is high, multiplying power is good, the secondary electricity of water system sodium ion having extended cycle life
Pond.
Realize that the technical solution of the object of the invention is as follows：
Water system sodium ion secondary battery, including anode, cathode, membrane and electrolyte, the active material of the anode is
Prussian Zn3[Fe(CN)6]2, the active material of the cathode is titanium phosphate sodium, the solute of the electrolyte
For sodium perchlorate and polyethylene glycol.
Preferably, the molar ratio of the sodium perchlorate and polyethylene glycol is 5~7:2~4.
Preferably, the molar concentration of the sodium perchlorate is 9mol/L~10mol/L.
The active material Prussian Zn of the anode3[Fe(CN)6]2, prepared by following steps：First
Sodium oxalate and zinc salt are reacted, treat after reaction, to be slow added into cyanide salt, washing and drying are to get Zn3[Fe(CN)6]2。
The zinc salt is selected from ZnSO4、Zn(NO3)2Or ZnCl2, concentration is 0.06mol/L~1mol/L.
The cyanide salt is selected from K3[Fe(CN)6]、Na3[Fe(CN)6]、K4[Fe(CN)6] or Na4[Fe(CN)6], it is optimal
Elect K as3[Fe(CN)6]、Na3[Fe(CN)6], concentration is 0.05mol/L~0.1mol/L.
The sodium oxalate and zinc salt reaction time for 1.5 it is small when~5 it is small when.
The reaction temperature is 25 DEG C~35 DEG C.
Compared with prior art, the present invention has the following advantages：
(1) in aqueous electrolyte, by adding in polyethylene glycol, it is high aqueous electrolyte intermediate ion mobility had both been maintained
Advantage, and drastically increase the operating voltage window of electrolyte stabilization；In addition, it also has centainly the stability of electrode material
Facilitation；
(2) water system sodium ion secondary battery of the invention has the chemical property of high voltage, high magnification and high stability,
Under the electric current of 1C=60mA/g carry out charge-discharge performance test, operating voltage be 1.6V~1.65V, multiplying power can reach 40C with
Upper and period hundred times, for coulombic efficiency close to 100%, capacity retention ratio is more than 90%.
Description of the drawings
Fig. 1 is the Zn that embodiment 1 synthesizes3[Fe(CN)6]2The scanning electron microscope (SEM) photograph of particle.
Fig. 2 is the Zn that embodiment 1 synthesizes3[Fe(CN)6]2Charging and discharging curve figure.
Fig. 3 is the high rate performance graph for the aqoue seconary battery that embodiment 1 is built.
Fig. 4 is the cycle performance of aqoue seconary battery and the relational graph of coulombic efficiency that embodiment 1 is built.
Specific embodiment
With reference to embodiment and attached drawing, the invention will be further described.Such as without specific instruction of the present invention, use
Conventional method known to the art.
Embodiment 1
Weigh 1.08g Zinc vitriols, 5.36g sodium oxalates and the 1.65g potassium ferricyanides；They are configured to concentration successively
For the aqueous solution of 0.075mol/L, 0.2mol/L and 0.005mol/L；Zinc sulfate and sodium oxalate water solution are fed first into
In ionized water, after complete reaction, then potassium ferricyanide aqueous solution is slowly added, after still aging 2h, you can obtain reaction product；
Obtained reaction product is washed repeatedly repeatedly with deionized water afterwards, finally at 100 DEG C, dry 12h obtains Zn3[Fe
(CN)6]2Solid.
Zn obtained3[Fe(CN)6]2Solid is stood as shown in Figure 1, can be seen that ZnHCF particles from scanning electron microscope (SEM) photograph and have
Cube pattern, and an even property is preferable；Its particle size distribution is uniform, at 1-2 μm or so.In this particle with highly crystalline
In, it is more advantageous to the migration of sodium ion and the stability of material.
Using N-Methyl pyrrolidone as dispersant, Zn that 0.8g is prepared in above-mentioned3[Fe(CN)6]2, 0.1g acetylene
After black and 0.1g Kynoar is mixed evenly in the circular titanium net coated on a diameter of 1.3cm, at 80 DEG C, drying system
Obtain zinc-iron cyanide electrode slice.
Using N-Methyl pyrrolidone as dispersant, titanium phosphate sodium that 0.8g is prepared in above-mentioned, 0.1g acetylene blacks with
After 0.1g Kynoar is mixed evenly in the circular titanium net coated on a diameter of 1.3cm, at 80 DEG C, dries and phosphorus is made
Sour titanium sodium electrode slice.
The formula of electrolyte：Sodium perchlorate, polyethylene glycol (molar ratio 5 are weighed respectively:2) it is added in deionized water,
Wherein the molar concentration of sodium perchlorate is 10mol/L, is stirred, until as the liquid of water white transparency.
As shown in Figure 2, the Zn synthesized by above method3[Fe(CN)6]2Material show in the electrolytic solution one compared with
High voltage platform (0.95V vs.Ag/AgCl) and reversible capacity (66mAh/g).Illustrate Zn3[Fe(CN)6]2With excellent
Chemical property.
Using zinc-iron cyanide electrode slice obtained above as anode, titanium phosphate sodium electrode slice is cathode, with sodium perchlorate and
The aqueous solution of polyethylene glycol is electrolyte, and glass fibre membrane obtains water system sodium ion secondary battery as membrane, assembling.
The water system sodium ion secondary battery obtained to assembling carries out charge-discharge test under the constant current of 1C, obtains battery
Operating voltage is up to 1.6V.
From the figure 3, it may be seen that the water system sodium-ion battery built with this carries out charge-discharge test under the up to multiplying power of 40C,
Capacity is maintained at 75% or so of 1C capacity, illustrates that the water system battery has excellent high rate performance.
As shown in Figure 4, the cycle charge discharge electrical testing of 100 times is being passed through with the water system sodium ion secondary battery that this builds,
For capacity retention ratio more than 90%, coulombic efficiency close to 100%, illustrates that the stability of the water system battery is fine always.
Embodiment 2
The present embodiment is substantially the same manner as Example 1, the difference is that, the molar concentration of sodium perchlorate is in electrolyte
9mol/L builds a kind of water system sodium-ion battery in the method for embodiment 1.The water system sodium ion secondary battery obtained to assembling exists
Charge-discharge test is carried out under the constant current of 1C, the operating voltage for obtaining battery is up to 1.6V.The secondary electricity of water system sodium ion of structure
Pond is by the cycle charge discharge electrical testing of 100 times, and capacity retention ratio 91% or so, close to 100%, say always by coulombic efficiency
The stability of the bright water system battery is fine.The water system sodium-ion battery of structure carries out charge-discharge test under the up to multiplying power of 40C,
Its capacity is maintained at more than the 74% of 1C capacity, illustrates that the water system battery has excellent high rate performance.
Comparative example 1
This comparative example is substantially the same manner as Example 1, the difference is that, without polyethylene glycol additive in electrolyte, with reality
The method for applying example 1 builds a kind of water system sodium-ion battery.1.6V is up to the operating voltage for assembling obtained aqoue seconary battery
Left and right, by the cycle charge discharge electrical testing of 100 times, capacity retention ratio is 74%, coulombic efficiency 96%.Pass through the comparative example
As can be seen that in the case of no polyethylene glycol additive, the cycle performance of battery has one to greatly reduce.
Comparative example 2
This comparative example is same as Example 1, the difference is that, the molar concentration of sodium perchlorate is 5mol/ in electrolyte
L builds a kind of water system sodium-ion battery in the method for embodiment 1.To the operating voltage height for the aqoue seconary battery that assembling obtains
Up to 1.5V or so, in the cycle charge discharge electrical testing by 100 times, capacity retention ratio is 83%, coulombic efficiency 96%.By this
Comparative example can be seen that in the sodium ion electrolyte of high concentration, be conducive to improve the voltage and cyclical stability of battery.
Comparative example 3
This comparative example is same as Example 1, the difference is that, the molar concentration of sodium perchlorate is 12mol/L.
A kind of water system sodium-ion battery is built in the method for embodiment 1.Work to the aqoue seconary battery that assembling obtains
Voltage is up to 1.6V or so；Charge-discharge test is carried out under the up to multiplying power of 40C, capacity is maintained at the 68% of 1C capacity.It is logical
It crosses the comparative example to can be seen that in the sodium ion electrolyte of higher concentration, is unfavorable for the migration of sodium ion, reduces battery
High rate performance.
Claims (8)
1. water system sodium ion secondary battery, including anode, cathode, membrane and electrolyte, which is characterized in that the work of the anode
Property material be Prussian Zn3[Fe(CN)6]2, the active material of the cathode is titanium phosphate sodium, the electrolysis
The solute of liquid is sodium perchlorate and polyethylene glycol.
2. water system sodium ion secondary battery according to claim 1, which is characterized in that the sodium perchlorate and poly- second two
The molar ratio of alcohol is 5~7:2~4.
3. water system sodium ion secondary battery according to claim 1, which is characterized in that the sodium perchlorate it is mole dense
It spends for 9mol/L~10mol/L.
4. water system sodium ion secondary battery according to claim 1, which is characterized in that the active material of the anode is general
Shandong scholar's indigo plant compound Zn3[Fe(CN)6]2, prepared by following steps：Sodium oxalate and zinc salt are reacted first, to the end of reaction
Afterwards, cyanide salt is slow added into, washing and drying are to get Zn3[Fe(CN)6]2。
5. water system sodium ion secondary battery according to claim 1, which is characterized in that the zinc salt is selected from ZnSO4、Zn
(NO3)2Or ZnCl2, concentration is 0.06mol/L~1mol/L.
6. water system sodium ion secondary battery according to claim 1, which is characterized in that the cyanide salt is selected from K3[Fe
(CN)6]、Na3[Fe(CN)6]、K4[Fe(CN)6] or Na4[Fe(CN)6], it is most preferably K3[Fe(CN)6]、Na3[Fe(CN)6], it is dense
It spends for 0.05mol/L~0.1mol/L.
7. water system sodium ion secondary battery according to claim 1, which is characterized in that the sodium oxalate and zinc salt reaction
Time for 1.5 it is small when~5 it is small when.
8. water system sodium ion secondary battery according to claim 1, which is characterized in that the reaction temperature for 25 DEG C~
35℃。
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| CN201711347820.8A CN108054443A (en) | 2017-12-15 | 2017-12-15 | Water system sodium ion secondary battery |
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| CN201711347820.8A CN108054443A (en) | 2017-12-15 | 2017-12-15 | Water system sodium ion secondary battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878877A (en) * | 2018-07-03 | 2018-11-23 | 中国科学院宁波材料技术与工程研究所 | A kind of water system zinc ion cathode active material for secondary battery and a kind of water system zinc ion secondary cell |
| CN110048104A (en) * | 2019-04-16 | 2019-07-23 | 浙江大学 | A kind of water system battery and preparation method thereof based on cyaniding frame material |
| CN111313017A (en) * | 2019-11-29 | 2020-06-19 | 合肥工业大学 | Calcium ion battery anode material and preparation method and application thereof |
| CN113140807A (en) * | 2021-04-21 | 2021-07-20 | 浙江大学 | Water battery with incombustibility |
| CN113725500A (en) * | 2021-09-03 | 2021-11-30 | 中南大学 | Mixed electrolyte of water-based zinc ion battery |
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| CN103022577A (en) * | 2012-12-27 | 2013-04-03 | 武汉大学 | Water system chargeable sodium-ion battery |
| JP2014053190A (en) * | 2012-09-07 | 2014-03-20 | Nippon Telegr & Teleph Corp <Ntt> | Sodium secondary battery |
| CN106745068A (en) * | 2016-12-12 | 2017-05-31 | 华中科技大学 | A kind of preparation method and applications of the nanometer Prussian Blue of low defect |
| CN107256986A (en) * | 2017-07-27 | 2017-10-17 | 中国科学院宁波材料技术与工程研究所 | A kind of aqueous electrolyte and Water based metal ion battery |
-
2017
- 2017-12-15 CN CN201711347820.8A patent/CN108054443A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014053190A (en) * | 2012-09-07 | 2014-03-20 | Nippon Telegr & Teleph Corp <Ntt> | Sodium secondary battery |
| CN103022577A (en) * | 2012-12-27 | 2013-04-03 | 武汉大学 | Water system chargeable sodium-ion battery |
| CN106745068A (en) * | 2016-12-12 | 2017-05-31 | 华中科技大学 | A kind of preparation method and applications of the nanometer Prussian Blue of low defect |
| CN107256986A (en) * | 2017-07-27 | 2017-10-17 | 中国科学院宁波材料技术与工程研究所 | A kind of aqueous electrolyte and Water based metal ion battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878877A (en) * | 2018-07-03 | 2018-11-23 | 中国科学院宁波材料技术与工程研究所 | A kind of water system zinc ion cathode active material for secondary battery and a kind of water system zinc ion secondary cell |
| CN110048104A (en) * | 2019-04-16 | 2019-07-23 | 浙江大学 | A kind of water system battery and preparation method thereof based on cyaniding frame material |
| CN110048104B (en) * | 2019-04-16 | 2020-10-13 | 浙江大学 | Water-based battery based on cyaniding frame material and preparation method thereof |
| CN111313017A (en) * | 2019-11-29 | 2020-06-19 | 合肥工业大学 | Calcium ion battery anode material and preparation method and application thereof |
| CN113140807A (en) * | 2021-04-21 | 2021-07-20 | 浙江大学 | Water battery with incombustibility |
| CN113725500A (en) * | 2021-09-03 | 2021-11-30 | 中南大学 | Mixed electrolyte of water-based zinc ion battery |
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Application publication date: 20180518 |