CN108336353B - Mixed lithium/sodium ion battery - Google Patents
Mixed lithium/sodium ion battery Download PDFInfo
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- CN108336353B CN108336353B CN201810010855.0A CN201810010855A CN108336353B CN 108336353 B CN108336353 B CN 108336353B CN 201810010855 A CN201810010855 A CN 201810010855A CN 108336353 B CN108336353 B CN 108336353B
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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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- 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 a mixed lithium/sodium ion battery, wherein the anode material is a sodium-based material which can be used as the anode material of a lithium ion battery, and the molecular formula of the anode material is Na3(VO)2(PO4)2And F, the cathode material is a common cathode material of the lithium ion battery. The mass ratio of active substances of positive and negative pole pieces in the mixed lithium/sodium ion battery is 2.0-3.0, and the electrolyte is 1M LiPF6(volume ratio: 1: 1)/EC + DMC + DEC, LiPF6EC + DMC (volume ratio 1:1), LiPF6and/EC + DEC (volume ratio 1: 1). The hybrid lithium/sodium ion battery provided by the invention has the advantages of low price, excellent electrochemical performance, good performance in a low-temperature environment and wide application range.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries and electrochemistry, and particularly relates to a mixed lithium/sodium ion battery which is low in price, excellent in electrochemical performance and wide in application range.
Background
Lithium ion batteries have important and wide applications in energy storage, ranging from portable electronic devices, such as notebook computers and mobile phones, to increasingly electric vehicles, hybrid vehicles, and large-scale energy storage, due to their advantages of long cycle life, high energy density, safety, stability, no memory effect, and the like. But the cost of the application is high and the universality is limited due to the low abundance of the lithium element in the earth crust. The sodium element and the lithium element are located in the same main group, and the chemical and physical properties of the sodium element and the lithium element are similar, so that the sodium ion battery and the lithium ion battery have similar working principle and energy storage mechanism, and the sodium resource has abundant reserve and wide distribution, and is expected to be used as a substitute of the lithium ion battery. However, due to Na+Ionic radius ratio of (5) Li+Large, so that the reversible deintercalation process of sodium ions in the electrode material is limited, thereby affecting the electrochemical performance of the battery. Therefore, it is necessary to overcome the disadvantages of the sodium ion battery while fully utilizing the advantages of the lithium ion battery.
A hybrid lithium/sodium ion battery should be an efficient design to achieve this goal. In 2006, j.baker et al put forward the concept of a hybrid lithium ion battery for the first time, and research shows that a sodium-based material and a conventional lithium ion positive electrode material have a similar lithium storage mechanism. Currently, hybrid lithium/sodium ion batteries have attracted considerable attention using lithium-free compounds as low-cost electrode materials for conventional lithium ion batteries. In general, hybrid lithium/sodium ion batteries exhibit better electrochemical performance than sodium ion batteries and are less expensive than lithium ion batteries.
The sodium-based compound fluoro sodium vanadyl phosphate is used as the anode material of the lithium ion battery, and the lithium ion battery contains LiPF6The organic electrolyte is matched with common cathode materials of the lithium ion battery to assemble the mixed lithium/sodium ion battery, and the mixed lithium/sodium ion battery shows good electrochemical performance.
Disclosure of Invention
The invention aims to provide a mixed lithium/sodium ion battery which has the characteristics of low price, excellent electrochemical performance and wide application range.
The anode material is a sodium-based material, can be used as an anode material of a lithium ion battery, and has a molecular formula of Na3(VO)2(PO4)2F, also writable as Na3V2O2(PO4)2F、Na3V2(PO4)2O2F、Na3{V2O2F[PO4]2} or FNa3[PO4]2[VO]2Space group I4/mmm belongs to the tetragonal system.
The method is realized by the following technical scheme:
a mixed lithium/sodium ion battery comprises a shell, a positive pole piece, a negative pole piece, a diaphragm and electrolyte, wherein the positive pole piece comprises a positive active substance, a binder and a conductive agent; the negative pole piece comprises a negative active material, a binder and a conductive agent; the electrolyte is an organic electrolyte commonly used by lithium ion batteries.
The positive electrode active material and the negative electrode active material are each a sodium-based material Na as described above3(VO)2(PO4)2F, common cathode materials of lithium ion batteries, such as graphite, lithium titanate, alloy materials and the like.
As mentioned above, the positive active material accounts for 70-90% of the total mass of the positive pole piece coating, and the negative active material accounts for 80-90% of the mass of the negative pole piece coating.
The electrolyte is an organic electrolyte commonly used for lithium ion batteries and comprises 1M LiPF6(volume ratio: 1: 1)/EC + DMC + DEC, LiPF6EC + DMC (volume ratio 1:1), LiPF6and/EC + DEC (volume ratio 1: 1).
The mass ratio of the active material of the positive pole piece to the active material of the negative pole piece is 2.2-3.0.
The invention provides a sodium-based material Na3V2(PO4)2O2The F is used in a lithium ion battery, and a mixed lithium/sodium ion battery formed by the F and a negative electrode shows excellent electrochemical performance by matching the active quality of a positive electrode plate and a negative electrode plate, and the mixed lithium/sodium ion battery has good performance in a low-temperature environment, so that the application range of the mixed lithium/sodium ion battery is widened.
The reaction temperature of the heat treatment in the step (4) can be 400-600 ℃, and the time can be 2-6 h.
Drawings
FIG. 1 electrochemical performance of example 1 (a) rate performance, (b) and (c) cycle performance;
FIG. 2 electrochemical performance of example 8 (a) performance at different temperatures vs. (b) -cycle performance at 25 ℃.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
The button cell is taken as an example for description, and the cell comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte. In the positive pole piece, the positive active substance is Na3V2(PO4)2O2F, the mass ratio of the active substance in the pole piece coating is 70-90%, the mass ratio of the conductive agent is 5-20%, and the mass ratio of the binder is 5-10%. Most preferred for this example is: na (Na)3V2(PO4)2 O 280% of F, 10% of acetylene black as a conductive agent and 10% of sodium carboxymethyl cellulose as a binder. In the negative pole piece, the negative active substance accounts for 80-90% by mass, the conductive agent accounts for 5-10% by mass and the binder accounts for 5-10% by mass in the pole piece coating. Most preferred for this example is: 80% of negative electrode active material, 10% of conductive agent acetylene black and 10% of binder sodium carboxymethyl cellulose.
Example 1
The negative electrode material is graphite, the mass ratio of the positive electrode plate active substance to the negative electrode plate active substance is 2.7:1.0, and the positive electrode plate active substance and the negative electrode plate active substance are 1M LiPF6DMC, DEC (volume ratio of 1:1) electrolyte and a glass fiber diaphragm are assembled into a button cell in a glove box, and then a constant current charge and discharge test is carried out on LAND at room temperature. The voltage interval is 2.8-4.4V.
Example 2
The negative electrode material is lithium titanate, the mass ratio of the active substance of the positive electrode plate to the active substance of the negative electrode plate is 1.3:1.0, and the LiPF is 1M6DMC, DEC (volume ratio of 1:1) electrolyte and a glass fiber diaphragm are assembled into a button cell in a glove box, and then a constant current charge and discharge test is carried out on LAND at room temperature. The voltage interval is 2.8-4.4V.
Example 3
The negative electrode material is made of silicon material (such as Si/C nano composite), and the mass ratio of the active substance of the positive electrode plate to the active substance of the negative electrode plate is 6.6:1.0, 1M LiPF6DMC, DEC (volume ratio of 1:1) electrolyte and a glass fiber diaphragm are assembled into a button cell in a glove box, and then a constant current charge and discharge test is carried out on LAND at room temperature. The voltage interval is 2.8-4.4V.
Example 4
The negative electrode material is graphite, the mass ratio of the positive electrode plate active substance to the negative electrode plate active substance is 3.0:1.0, and 1M LiPF6DMC, DEC (volume ratio of 1:1) electrolyte and a glass fiber diaphragm are assembled into a button cell in a glove box, and then a constant current charge and discharge test is carried out on LAND at room temperature. The voltage interval is 2.8-4.4V.
Example 5
Selection of cathode materialGraphite, positive and negative electrodes with the mass ratio of the active material of the positive electrode plate to the active material of the negative electrode plate being 2.2:1.0, and 1M LiPF6DMC, DEC (volume ratio of 1:1:1) electrolyte and a glass fiber diaphragm are assembled into a button cell in a glove box, and then a constant current charge and discharge test is carried out on LAND at room temperature. The voltage interval is 2.8-4.4V.
Example 6
The negative electrode material is graphite, the mass ratio of the positive electrode plate active substance to the negative electrode plate active substance is 2.7:1.0, and the positive electrode plate active substance and the negative electrode plate active substance are 1M LiPF6EC, DMC (volume ratio of 1:1) electrolyte and a glass fiber diaphragm are assembled into a button cell in a glove box, and then a constant current charge and discharge test is carried out on LAND at room temperature. The voltage interval is 2.8-4.4V.
Example 7
The negative electrode material is graphite, the mass ratio of the positive electrode plate active substance to the negative electrode plate active substance is 2.7:1.0, and the positive electrode plate active substance and the negative electrode plate active substance are 1M LiPF6EC (EC) and DEC (volume ratio of 1:1) electrolyte and a glass fiber diaphragm are assembled into a button cell in a glove box, and then a constant-current charge-discharge test is carried out on LAND at room temperature. The voltage interval is 2.8-4.4V.
TABLE 1 summary of the capacities of the materials of the examples
Example 8
The negative electrode material is graphite, the mass ratio of the positive electrode plate active substance to the negative electrode plate active substance is 2.7:1.0, and the positive electrode plate active substance and the negative electrode plate active substance are 1M LiPF6DMC, DEC (volume ratio of 1:1:1) electrolyte and a glass fiber diaphragm are assembled into a button cell in a glove box, and then constant current charge and discharge tests are respectively carried out at the temperature range of 25 ℃ to-25 ℃ and the current density of 0.013A/g. The voltage interval is 2.8-4.4V. The results are shown in Table 2 and FIG. 2.
Table 2 summary of discharge capacities of example 8 hybrid ion batteries at different test temperatures
Example 9Na3V2(PO4)2F3As the positive electrode material of sodium-based lithium ion battery
Mixing Na3V2(PO4)2F3Graphite as a negative electrode as a positive electrode, and LiPF of 2:1, 1M in mass ratio of positive and negative electrode sheet active materials6DMC (mass ratio of 2:1) as electrolyte, glass fiber (Whatman, Grade GF/A) as diaphragm, assembled into button cell in glove box, and then tested for constant current charging and discharging at 23 ℃. The voltage interval is 2.5-4.6V. The results are shown in Table 3
Table 3 discharge capacity of the material of example 7
Claims (8)
1. A mixed ion battery is characterized in that a sodium-based material is used as a positive electrode material of a lithium ion battery and is assembled with a negative electrode of the lithium ion battery to form a mixed lithium/sodium ion full battery, and an electrolyte is an organic electrolyte containing LiPF 6;
the sodium-based material is fluorinated sodium vanadium oxide phosphate, the molecular formula is Na3(VO)2(PO4)2F, the space group I4/mmm belongs to a tetragonal system;
the active substance of the negative electrode of the lithium ion battery is graphite, lithium titanate or a Si/C compound.
2. A hybrid ion battery as defined in claim 1, wherein: the lithium ion battery comprises a shell, a positive pole piece, a negative pole piece, a diaphragm and electrolyte, wherein the positive pole piece comprises a positive active material, a binder and a conductive agent; the negative pole piece comprises a negative active material, a binder and a conductive agent.
3. The hybrid ion battery of claim 2, wherein the negative electrode material is graphite, and the negative electrode material is characterized in that: the mass ratio of active substances of the positive and negative pole pieces is 2.2-3.0.
4. A hybrid ion battery as defined in claim 2, wherein: the negative electrode material is graphite, and the mass ratio of active substances of the positive and negative electrode plates is 2.6-2.8.
5. The hybrid ion battery of claim 2, wherein the negative electrode material is graphite, and the negative electrode material is characterized in that: the mass ratio of active substances of the positive and negative pole pieces is 2.7.
6. A hybrid ion battery as defined in claim 1, 2, 3, 4 or 5, wherein: the electrolyte is 1MLiPF6/EC + DMC + DEC in a volume ratio of 1:1:1, 1M LiPF6/EC + DMC in a volume ratio of 1:1, or 1M LiPF6/EC + DEC in a volume ratio of 1: 1.
7. A hybrid ion battery as defined in claim 6, wherein: is applied in the environment of 25 ℃ to-25 ℃.
8. Application of a sodium-based material Na3(VO)2(PO4)2F in an electrode material of a lithium ion battery or a mixed lithium/sodium ion battery.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020069618A1 (en) * | 2018-10-02 | 2020-04-09 | HYDRO-QUéBEC | Electrode materials comprising a lamellar oxide of sodium and of metal, electrodes comprising same and use of same in electrochemistry |
| 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 |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306771A (en) * | 2011-08-17 | 2012-01-04 | 中南大学 | Preparation method of vanadium sodium fluophosphate cathode material of hybrid ion battery |
| CN203445193U (en) * | 2013-08-20 | 2014-02-19 | 宋维鑫 | Secondary battery with mixed ions |
| CN104769757A (en) * | 2012-11-08 | 2015-07-08 | 丰田自动车株式会社 | Positive electrode active material and hybrid ion battery |
| JP2016076422A (en) * | 2014-10-08 | 2016-05-12 | トヨタ自動車株式会社 | Hybrid ion battery system |
| CN107482179A (en) * | 2017-07-10 | 2017-12-15 | 三峡大学 | A kind of anode material for lithium-ion batteries Na without lithium3V2(PO4)3/ C and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306771A (en) * | 2011-08-17 | 2012-01-04 | 中南大学 | Preparation method of vanadium sodium fluophosphate cathode material of hybrid ion battery |
| CN104769757A (en) * | 2012-11-08 | 2015-07-08 | 丰田自动车株式会社 | Positive electrode active material and hybrid ion battery |
| CN203445193U (en) * | 2013-08-20 | 2014-02-19 | 宋维鑫 | Secondary battery with mixed ions |
| JP2016076422A (en) * | 2014-10-08 | 2016-05-12 | トヨタ自動車株式会社 | Hybrid ion battery system |
| CN107482179A (en) * | 2017-07-10 | 2017-12-15 | 三峡大学 | A kind of anode material for lithium-ion batteries Na without lithium3V2(PO4)3/ C and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Hybrid-Ion A Lithium-Ion Cell Based on a Sodium Insertion Material";J. Barker etal.，;《Electrochemical and Solid-State Letters》;20060208;第9卷;见摘要,以及第A190页左栏第2-3段 * |
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