CN108336353A - One kind mixing lithium/sodium-ion battery - Google Patents
One kind mixing lithium/sodium-ion battery Download PDFInfo
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- CN108336353A CN108336353A CN201810010855.0A CN201810010855A CN108336353A CN 108336353 A CN108336353 A CN 108336353A CN 201810010855 A CN201810010855 A CN 201810010855A CN 108336353 A CN108336353 A CN 108336353A
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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Abstract
The invention discloses one kind to mix lithium/sodium-ion battery, and wherein positive electrode is sodium-based material, can be used as anode material for lithium-ion batteries, molecular formula Na3(VO)2(PO4)2F, negative material are the common negative material of lithium ion battery.The active material mass ratio of positive/negative plate is 2.0 3.0 in the mixing lithium/sodium-ion battery, and electrolyte is 1M LiPF6/ EC+DMC+DEC (volume ratios 1:1:1), LiPF6/ EC+DMC (volume ratios 1:1), LiPF6/ EC+DEC (volume ratios 1:1) etc..Mixing lithium/sodium-ion battery provided by the invention is cheap, electrochemical performance, and also with good performance at low ambient temperatures, has widened its scope of application.
Description
Technical field
The invention belongs to lithium ion batteries and electrochemical technology field, and in particular to a kind of cheap, chemical property
Mixing lithium/sodium-ion battery excellent, applied widely.
Background technology
The advantages that lithium ion battery is because with long circulation life, high-energy density, safety and stability and memory-less effect, in energy
There is important role in terms of amount storage and be widely used, from portable electronic device, such as laptop and mobile phone,
To growing electric vehicle, hybrid vehicle and extensive energy storage.But due in the earth's crust lithium abundance it is low,
The cost of its application is higher and popularity is restricted.And sodium element is located at same main group with elemental lithium, their chemistry, physics
Property is similar, so sodium-ion battery has similar operation principle and energy storage mechnism, and sodium resource reserve with lithium ion battery
It is abundant, widely distributed, it is expected to the replacer as lithium ion battery.However, due to Na+Ionic radius ratio Li+Greatly, so limit
Reversible deintercalation process of the sodium ion in electrode material is made, to influence the chemical property of battery.Therefore, it is giving full play to
While lithium ion battery advantage, the shortcomings that overcoming sodium-ion battery is very necessary.
Mixing lithium/sodium-ion battery should be an effective design for realizing this target.2006, J.Baker etc.
People has been put forward for the first time the concept of mixed type lithium ion battery, studies have shown that sodium-based material has with conventional lithium ion positive electrode
Similar storage lithium mechanism.Currently, mixing lithium/sodium-ion battery uses the compound without lithium as the low of conventional lithium ion battery
Cost electrode material has caused strong concern.Usually mixing lithium/sodium-ion battery is shown compared with sodium-ion battery
Preferable chemical property, it is cheap compared with lithium ion battery.
This patent is using sodium compound fluorophosphate vanadium oxygen sodium as anode material for lithium-ion batteries, using containing LiPF6's
Organic electrolyte, with the matching of lithium ion battery common negative material, be assembled into and mix lithium/sodium-ion battery, show good
Chemical property.
Invention content
It is an object of the present invention to provide a kind of mixing lithium/sodium-ion batteries, and show that cheap, chemical property is excellent
Feature different, applied widely.
Positive electrode in the present invention is sodium-based material, can be used as anode material for lithium-ion batteries, molecular formula Na3
(VO)2(PO4)2F can also be written as Na3V2O2(PO4)2F、Na3V2(PO4)2O2F、Na3{V2O2F[PO4]2Or FNa3[PO4]2
[VO]2, space group I4/mmm belongs to tetragonal crystal system.
The method of the present invention is achieved through the following technical solutions：
A kind of mixing lithium/sodium-ion battery, including shell, anode pole piece, cathode pole piece, diaphragm and electrolyte, it is described just
Pole pole piece includes positive active material, binder and conductive agent；The cathode pole piece includes negative electrode active material, binder and leads
Electric agent；The electrolyte is the general organic electrolyte of lithium ion battery.
Positive active material and negative electrode active material as described above are sodium-based material Na respectively3(VO)2(PO4)2F and lithium from
The sub- common negative material of battery, such as graphite, lithium titanate and alloy material.
Positive active material as described above accounts for the 70-90% of anode pole piece coating gross mass, and negative electrode active material accounts for cathode
The 80-90% of pole piece coating quality.
Electrolyte as described above is the general organic electrolyte of lithium ion battery, including 1M LiPF6/ EC+DMC+DEC (bodies
Product ratio 1:1:1), LiPF6/ EC+DMC (volume ratios 1:1), LiPF6/ EC+DEC (volume ratios 1:1) etc..
Anode pole piece active material as described above is 2.2-3.0 with negative electrode active material mass ratio.
The present invention is proposed sodium-based material Na3V2(PO4)2O2F is used in lithium ion battery, and the mixing lithium formed with cathode/
Sodium-ion battery shows excellent chemical property, and the mixing lithium/sodium by matching the active mass of positive and negative electrode piece
Ion battery is also with good performance at low ambient temperatures, has widened its scope of application.
It can be 400-600 DEG C that step (4), which is heat-treated reaction temperature, and the time can be 2-6h.
Description of the drawings
Chemical property (a) high rate performance of Fig. 1 embodiments 1, (b) and (c) cycle performance；
Performance comparison under chemical property (a) different temperatures of Fig. 2 embodiments 8, (b) cycle performance at -25 DEG C.
Specific implementation mode
With reference to embodiment, the present invention will be further described, but the invention is not limited in following embodiments.
Description is illustrated by taking button cell as an example, which includes anode pole piece, cathode pole piece, diaphragm, electrolyte.
In anode pole piece, positive active material Na3V2(PO4)2O2F, it is 70-90% that active material, which accounts for mass ratio, in pole piece coating, is led
Electric agent accounts for mass ratio 5-20%, and binder accounts for mass ratio 5-10%.This example is most preferably：Na3V2(PO4)2O2F is 80%, conductive
Agent acetylene black is 10%, and binder sodium carboxymethylcellulose is 10%.In cathode pole piece, negative electrode active material is in pole piece coating
In account for mass ratio 80-90%, conductive agent accounts for mass ratio 5-10%, and binder accounts for mass ratio 5-10%.This example is most preferably：Cathode
Active material is 80%, conductive agent acetylene black 10%, binder sodium carboxymethylcellulose 10%.
Embodiment 1
Negative material selects graphite, by anode pole piece active material and cathode pole piece active material mass ratio=2.7:1.0
Positive and negative anodes, 1M LiPF6EC:DMC:DEC (volume ratios 1:1) electrolyte, fibreglass diaphragm, are assembled into glove box
After button cell, constant current charge-discharge test is carried out on LAND at room temperature.Voltage range is 2.8-4.4V.
Embodiment 2
Negative material selects lithium titanate, by anode pole piece active material and cathode pole piece active material mass ratio=1.3:
1.0 positive and negative anodes, the LiPF of 1M6EC:DMC:DEC (volume ratios 1:1) electrolyte, fibreglass diaphragm, fill in glove box
After being made into button cell, constant current charge-discharge test is carried out on LAND at room temperature.Voltage range is 2.8-4.4V.
Embodiment 3
Negative material selects silicon materials (such as Si/C nano-complexes), by anode pole piece active material and cathode pole piece activity
Material mass ratio=6.6:1.0 positive and negative anodes, the LiPF of 1M6EC:DMC:DEC (volume ratios 1:1) electrolyte, glass fibre every
Film after being assembled into button cell in glove box, carries out constant current charge-discharge test on LAND at room temperature.Voltage range is 2.8-
4.4V。
Embodiment 4
Negative material selects graphite, by anode pole piece active material and cathode pole piece active material mass ratio=3.0:1.0
Positive and negative anodes, 1M LiPF6EC:DMC:DEC (volume ratios 1:1) electrolyte, fibreglass diaphragm, are assembled into glove box
After button cell, constant current charge-discharge test is carried out on LAND at room temperature.Voltage range is 2.8-4.4V.
Embodiment 5
Negative material selects graphite, by anode pole piece active material and cathode pole piece active material mass ratio=2.2:1.0
Positive and negative anodes, 1M LiPF6EC:DMC:DEC (volume ratios 1:1:1) electrolyte, fibreglass diaphragm, are assembled in glove box
After button cell, constant current charge-discharge test is carried out on LAND at room temperature.Voltage range is 2.8-4.4V.
Embodiment 6
Negative material selects graphite, by anode pole piece active material and cathode pole piece active material mass ratio=2.7:1.0
Positive and negative anodes, 1M LiPF6EC:DMC (volume ratios 1:1) electrolyte, fibreglass diaphragm, are assembled into button in glove box
After battery, constant current charge-discharge test is carried out on LAND at room temperature.Voltage range is 2.8-4.4V.
Embodiment 7
Negative material selects graphite, by anode pole piece active material and cathode pole piece active material mass ratio=2.7:1.0
Positive and negative anodes, 1M LiPF6EC:DEC (volume ratios 1:1) electrolyte, fibreglass diaphragm, are assembled into button in glove box
After battery, constant current charge-discharge test is carried out on LAND at room temperature.Voltage range is 2.8-4.4V.
The capacity of 1 each embodiment material of table summarizes
Embodiment 8
Negative material selects graphite, by anode pole piece active material and cathode pole piece active material mass ratio=2.7:1.0
Positive and negative anodes, 1M LiPF6EC:DMC:DEC (volume ratios 1:1:1) electrolyte, fibreglass diaphragm, are assembled in glove box
After button cell, respectively under 25 DEG C Dao -25 DEG C of temperature range, current density is that 0.013A/g carries out constant current charge-discharge survey
Examination.Voltage range is 2.8-4.4V.The result is shown in table 2 and Fig. 2.
Discharge capacity of 2 embodiment of table, the 8 hybrid ionic battery under different test temperatures summarizes
Embodiment 9Na3V2(PO4)2F3As sodium-base lithium ion cell positive material
By Na3V2(PO4)2F3As anode, graphite is as cathode, mass ratio=2 of positive and negative anodes pole piece active material:1,1M
LiPF6EC:DMC (mass ratioes 2:1) electrolyte, glass fibre (Whatman, Grade GF/A) is used as to be used as diaphragm,
After being assembled into button cell in glove box, constant current charge-discharge test is carried out at 23 DEG C.Voltage range is 2.5-4.6V.Its result
It is shown in Table 3
The discharge capacity of 3 embodiment of table, 7 material
Claims (10)
1. a kind of hybrid ionic battery, which is characterized in that using sodium-based material as anode material for lithium-ion batteries, with common lithium
Ion battery cathode is assembled into mixing lithium/sodium ion full battery business, and containing LiPF6Organic electrolyte in tested.
2. sodium base anode material according to claim 1, it is characterised in that Chinese is fluorophosphate vanadium oxygen sodium, point
Minor is Na3(VO)2(PO4)2F can also be written as Na3V2O2(PO4)2F、Na3V2(PO4)2O2F、Na3{V2O2F[PO4]2Or FNa3
[PO4]2[VO]2, space group I4/mmm belongs to tetragonal crystal system.
3. according to claims 1, the construction feature of the mixing lithium/sodium-ion battery includes shell, anode pole piece, cathode
Pole piece, diaphragm and electrolyte, the anode pole piece include positive active material, binder and conductive agent；The cathode pole piece packet
Include negative electrode active material, binder and conductive agent；The electrolyte is the general organic electrolyte of lithium ion battery.
4. positive active material according to claim 2 is Na3(VO)2(PO4)2F, the negative electrode active material are stone
Ink, lithium titanate and Si/C compounds, preferably graphite.
5. a kind of mixing lithium/sodium-ion battery according to claim 2, negative material selects graphite, it is characterised in that positive and negative
The active material mass ratio of pole piece is 2.2-3.0.
6. a kind of mixing lithium/sodium-ion battery according to claim 5, negative material selects graphite, it is characterised in that positive and negative
The active material mass ratio of pole piece is 2.6-2.8.
7. a kind of mixing lithium/sodium-ion battery according to claim 6, negative material selects graphite, it is characterised in that positive and negative
The active material mass ratio of pole piece is 2.7.
8. being 1M LiPF according to electrolyte described in claim 3-76/ EC+DMC+DEC (volume ratios 1:1:1), LiPF6/EC+DMC
(volume ratio 1:1), LiPF6/ EC+DEC (volume ratios 1:1) etc., preferably electrolyte 1M LiPF6/ EC+DMC+DEC (volume ratios 1:1:
1)。
9. according to a kind of mixing lithium/sodium-ion battery described in claim 1-8, it is characterised in that can also be applied to low temperature environment
(25 DEG C Dao -25 DEG C).
10. according to claim 1-9, sodium-based material Na3(VO)2(PO4)2F is in lithium ion battery and mixing lithium/sodium ion
Application in battery electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810010855.0A CN108336353B (en) | 2018-01-05 | 2018-01-05 | Mixed lithium/sodium ion battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810010855.0A CN108336353B (en) | 2018-01-05 | 2018-01-05 | Mixed lithium/sodium ion battery |
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| CN108336353B CN108336353B (en) | 2020-04-21 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112913052A (en) * | 2018-10-02 | 2021-06-04 | 魁北克电力公司 | Electrode material comprising layered sodium and an oxide of a metal, electrode comprising same and use thereof in electrochemistry |
| CN113046768A (en) * | 2021-03-15 | 2021-06-29 | 东北师范大学 | Potassium vanadyl fluorophosphate, preparation method and application thereof, and potassium ion battery |
| CN113299897A (en) * | 2021-06-02 | 2021-08-24 | 桂林电子科技大学 | Na3V2(PO4)3Mixed ion full cell with @ C as anode material |
| CN113871697A (en) * | 2021-09-28 | 2021-12-31 | 深圳市超壹新能源科技有限公司 | Sodium-lithium battery |
| CN113937336A (en) * | 2021-09-20 | 2022-01-14 | 复旦大学 | Wide-temperature mixed ion battery based on lithium iron phosphate anode and tin-carbon cathode |
| CN116093255A (en) * | 2023-02-20 | 2023-05-09 | 中国科学院长春应用化学研究所 | Battery system for evaluating lithium ion and sodium ion storage compatibility of positive electrode material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112913052A (en) * | 2018-10-02 | 2021-06-04 | 魁北克电力公司 | Electrode material comprising layered sodium and an oxide of a metal, electrode comprising same and use thereof in electrochemistry |
| CN113046768A (en) * | 2021-03-15 | 2021-06-29 | 东北师范大学 | Potassium vanadyl fluorophosphate, preparation method and application thereof, and potassium ion battery |
| CN113046768B (en) * | 2021-03-15 | 2023-07-21 | 东北师范大学 | Potassium vanadyl fluorophosphate, preparation method and application thereof, and potassium ion battery |
| CN113299897A (en) * | 2021-06-02 | 2021-08-24 | 桂林电子科技大学 | Na3V2(PO4)3Mixed ion full cell with @ C as anode material |
| CN113299897B (en) * | 2021-06-02 | 2023-06-02 | 桂林电子科技大学 | Na (Na) 3 V 2 (PO 4 ) 3 Mixed ion full battery with @ C as positive electrode material |
| CN113937336A (en) * | 2021-09-20 | 2022-01-14 | 复旦大学 | Wide-temperature mixed ion battery based on lithium iron phosphate anode and tin-carbon cathode |
| CN113871697A (en) * | 2021-09-28 | 2021-12-31 | 深圳市超壹新能源科技有限公司 | Sodium-lithium battery |
| CN116093255A (en) * | 2023-02-20 | 2023-05-09 | 中国科学院长春应用化学研究所 | Battery system for evaluating lithium ion and sodium ion storage compatibility of positive electrode material |
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