CN117954626A - High first effect sodium ion battery - Google Patents
High first effect sodium ion battery Download PDFInfo
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- CN117954626A CN117954626A CN202410082407.7A CN202410082407A CN117954626A CN 117954626 A CN117954626 A CN 117954626A CN 202410082407 A CN202410082407 A CN 202410082407A CN 117954626 A CN117954626 A CN 117954626A
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- Prior art keywords
- battery
- electrolyte
- sodium ion
- ratio
- ion battery
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 34
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 230000000694 effects Effects 0.000 title claims description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 239000011734 sodium Substances 0.000 claims abstract description 25
- 239000011149 active material Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 230000005501 phase interface Effects 0.000 claims abstract description 5
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 5
- 238000002347 injection Methods 0.000 claims abstract description 4
- 239000007924 injection Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 4
- 229920000447 polyanionic polymer Polymers 0.000 claims abstract description 4
- 229910000158 manganese(II) phosphate Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 11
- 229910052708 sodium Inorganic materials 0.000 abstract description 11
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 6
- 238000009831 deintercalation Methods 0.000 description 6
- 238000009830 intercalation Methods 0.000 description 6
- 230000002687 intercalation Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
Classifications
-
- 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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- Secondary Cells (AREA)
Abstract
The invention discloses a high first-effect sodium ion battery, which comprises an anode, a cathode and electrolyte, wherein the active materials of the anode and the cathode are respectively ion-deintercalated polyanion compounds, a solid electrolyte phase interface film and an electrochemical interface film are not generated at the interface of the anode and the cathode, and the first coulomb efficiency is more than 98%; the range of the NP ratio of the battery is 0.7-1.3; different electrolyte concentrations are designed according to different NP ratios, and the battery liquid injection coefficient is smaller than 3g/Ah; the electrolyte adopts non-aqueous electrolyte. The high first-efficiency sodium ion battery provided by the invention has the advantages that SEI film and CEI film are not generated, the first efficiency is high and is more than 98%, the energy loss is small, dendrite and sodium precipitation phenomena are not generated, and the NP ratio is free in design.
Description
Technical Field
The invention relates to a high first effect sodium ion battery.
Background
In the conventional lithium and sodium battery activation processes, the electrolyte solvent and lithium/sodium salt undergo side reactions, forming a solid electrolyte phase interface film (SEI) and an electrochemical interface film (CEI film) on the negative and positive electrodes of the battery, respectively. Although the formation of the SEI film and the CEI film may protect the lithium ion battery electrode and the electrolyte, it also has adverse effects such as increasing irreversible capacity for charge and discharge, decreasing charge and discharge efficiency of the electrode material, limiting diffusion rate of lithium/sodium ions, and the like. Meanwhile, in the battery cycle process, due to the existence of the volume effect, the electrode material is damaged and regenerated in the charge and discharge process, so that the SEI film and CEI film quality directly influence the performance and cycle life of the battery.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a high-first-efficiency sodium ion battery, wherein SEI films and CEI films are not generated, the first efficiency is high and is more than 98%, the energy loss is small, dendrite and sodium precipitation phenomena are not generated, and the NP ratio is free in design.
The technical scheme for achieving the purpose is as follows: the high first effect sodium ion battery comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that the active materials of the positive electrode and the negative electrode are respectively ion-deintercalated polyanion compounds, and a solid electrolyte phase interface film and an electrochemical interface film are not generated at the interface of the positive electrode and the negative electrode, so that the first coulombic efficiency is more than 98%; the range of the NP ratio of the battery is 0.7-1.3; different electrolyte concentrations are designed according to different NP ratios; the battery adopts a lean solution structure, and the liquid injection coefficient of the battery is less than 3g/Ah; the electrolyte adopts non-aqueous electrolyte.
The high first effect sodium ion battery, wherein the active material of the positive electrode is selected from at least one of Na4Fe3(PO4)2(P2O7)、Na4Fe3-x Mnx(PO4)2(P2O7)、Na4Mn3(PO4)2(P2O7) and Na 3MnTi(PO4)3, wherein X is more than 0 and less than 3;
the active material of the negative electrode is at least one selected from NaTi 2(PO4)3 and Na 3MnTi(PO4)3.
The high-first-efficiency sodium ion battery is characterized in that the NP ratio of the battery is free in design, and the range of the NP ratio of the battery is 0.8-1.2.
The high first effect sodium ion battery, wherein when the NP ratio of the battery is 0.8-1.0, the concentration of the electrolyte is 0.2-1 mol/kg.
The high first effect sodium ion battery, wherein when the NP ratio of the battery is 1.0-1.2, the concentration of the electrolyte is 1-5 mol/kg.
In the sodium ion battery with high first efficiency, the charge and discharge potential of the negative electrode is 2.1V.
The high first effect sodium ion battery of the invention has the following characteristics:
(1) Since the sodium intercalation potential of the anode active material is very high, the anode charge-discharge potential is 2.1V relative to a sodium metal electrode, so that SEI is not generated;
(2) In the first activation process of the battery, because electrolyte is not present and reacts with electrolyte salt, SEI film and CEI film are not generated, so that sodium ion consumption is avoided, sodium ions released from the positive electrode can be completely embedded into the negative electrode, the first effect is high, the first effect is more than 98%, and the energy loss is small;
(3) Because no SEI film and CEI film are generated, broken, regrown and the like, electrolyte salt is not consumed, and electrolyte only plays a role of a medium for ion transmission, a small amount of electrolyte can be used, the weight of the battery is reduced, and the specific energy of the quality is improved.
(4) Conventional lithium and sodium electricity designs require an excessive capacity of the negative electrode, i.e., an NP ratio of greater than 1, because dendrites and sodium and lithium precipitation phenomena are extremely easy to occur when the carbon-based negative electrode is insufficient in capacity, resulting in failure of the battery; according to the invention, as the negative electrode adopts the ion deintercalation compound instead of the carbon negative electrode, dendrite and sodium precipitation phenomena are not generated, so that the NP ratio is free to design;
(5) When the NP ratio is 0.8-1.0, the capacity of the negative electrode is lower than that of the positive electrode, and during normal charge and discharge, the sodium ions released from the positive electrode can meet the requirements of the intercalation and deintercalation of the negative electrode material, so that low-solubility electrolyte can be used, and the production cost is reduced; when the NP ratio is 1.0-1.2, the capacity of the negative electrode is higher than that of the positive electrode, and during normal charge and discharge, the sodium ions released from the positive electrode cannot meet the requirement of the intercalation and deintercalation of the negative electrode material, and high-concentration electrolyte is needed for supplementing the sodium ions, so that the production cost is higher, but the battery has high specific energy.
Drawings
FIG. 1 is an EIS spectrum of a battery of comparative example;
fig. 2 is an EIS spectrum of the battery of example 1.
Detailed Description
In order to enable those skilled in the art to better understand the technical scheme of the present invention, the following detailed description is provided with reference to the accompanying drawings:
The high first effect sodium ion battery comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that the active materials of the positive electrode and the negative electrode are respectively ion-deintercalated polyanion compounds, a solid electrolyte phase interface film and an electrochemical interface film are not generated at the interface of the positive electrode and the negative electrode, and the first coulomb efficiency is more than 98%; the range of the NP ratio of the battery is 0.7-1.3; the battery adopts a lean solution structure, and the liquid injection coefficient of the battery is less than 3g/Ah; the electrolyte adopts non-aqueous electrolyte.
Na 4Fe3(PO4)2(P2O7 is selected as the positive electrode active material), niti 2(PO4)3 is selected as the negative electrode active material,
Calibrating the anode and the cathode: the conductive material is acetylene black, the binder is MNP solution of PVDF (polyvinylidene fluoride) of 5wt.%, the proportion of the active material, the conductive agent and the binder is 80:10:10, a pole piece with the wet thickness of 200 micrometers is prepared by adopting a manual coating mode, after vacuum drying, a metal sodium piece is adopted as a counter electrode for testing, and the discharge specific capacity of the positive electrode is 109.75mAh/g and the discharge specific capacity of the negative electrode is 92.50mAh/g through calibration.
Examples 1 to 4: the conductive material was acetylene black, the binder was 5wt.% MNP (N-Methylpyrrolidone ) solution of PVDF (polyvinylidene difluoride, polyvinylidene fluoride), the slurry was prepared according to the ratio of active material, conductive agent and binder of 92:4:4, pole pieces of different wet thickness were prepared by hand coating according to the data in table 1, and after vacuum drying, full cells were assembled according to different anode-cathode ratios. Electrolyte solutions with different concentrations are selected for use, electrolyte salt in the electrolyte solution is sodium perchlorate, solvent is propylene carbonate, and the initial effect of the battery is tested.
Table 1, pole piece thickness and performance data table for examples 1-4:
Comparative example: positive electrode adopts Na 4Fe3(PO4)2(P2O7), and negative electrode adopts hard carbon to assemble the full cell.
Referring to fig. 1 and 2, the EIS test was performed after 10 cycles of the full cell of example 1 and the full cell of the comparative example, and it can be seen that the comparative example has a significant SEI formation, which is seen from the square frame portion of fig. 1, the ion diffusion resistance of this portion is SEI-induced, whereas example 1 has no SEI formation, and the ion diffusion resistance (the size of semicircle in fig. 2) of the battery is low because no SEI is generated, limiting the sodium ion diffusion rate.
The active material of the positive electrode of the high first effect sodium ion battery is at least one selected from Na4Fe3(PO4)2(P2O7)、Na4Fe3- xMnx(PO4)2(P2O7)、Na4Mn3(PO4)2(P2O7) and Na 3MnTi(PO4)3, wherein X is more than 0 and less than 3; the active material of the negative electrode is selected from at least one of NaTi 2(PO4)3 and Na 3MnTi(PO4)3. Since the sodium intercalation potential of the anode active material is very high, the anode charge-discharge potential is 2.1V relative to a sodium metal electrode, so that SEI is not generated; in the first activation process of the battery, because electrolyte is not present and reacts with electrolyte salt, SEI film and CEI film are not generated, so that sodium ion consumption is avoided, sodium ions released from the positive electrode can be completely embedded into the negative electrode, the first effect is high, the first effect is more than 98%, and the energy loss is small; because no SEI film and CEI film are generated, broken, regrown and the like, electrolyte salt is not consumed, and electrolyte only plays a role of a medium for ion transmission, a small amount of electrolyte can be used, the weight of the battery is reduced, and the specific energy of the quality is improved. Because the negative electrode adopts ion deintercalation compound instead of carbon negative electrode, dendrite and sodium precipitation phenomenon can not be generated, so NP ratio design is free; when the NP ratio is 0.8-1.0, the capacity of the negative electrode is lower than that of the positive electrode, and during normal charge and discharge, the sodium ions released from the positive electrode can meet the requirements of the intercalation and deintercalation of the negative electrode material, so that low-solubility electrolyte can be used, and the production cost is reduced; when the NP ratio is 1.0-1.2, the capacity of the negative electrode is higher than that of the positive electrode, and during normal charge and discharge, the sodium ions released from the positive electrode cannot meet the requirement of the intercalation and deintercalation of the negative electrode material, and high-concentration electrolyte is needed for supplementing the sodium ions, so that the production cost is higher, but the battery has high specific energy.
In conclusion, the high first-efficiency sodium ion battery provided by the invention has the advantages that SEI film and CEI film are not generated, the first efficiency is high and is more than 98%, the energy loss is small, dendrite and sodium precipitation phenomena are not generated, and the NP ratio is free in design.
It will be appreciated by persons skilled in the art that the above embodiments are provided for illustration only and not for limitation of the invention, and that variations and modifications of the above described embodiments are intended to fall within the scope of the claims of the invention as long as they fall within the true spirit of the invention.
Claims (6)
1. The high first effect sodium ion battery comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that the active materials of the positive electrode and the negative electrode are respectively ion-deintercalated polyanion compounds, and a solid electrolyte phase interface film and an electrochemical interface film are not generated at the interface of the positive electrode and the negative electrode, so that the first coulombic efficiency is more than 98%; the range of the NP ratio of the battery is 0.7-1.3; different electrolyte concentrations are designed according to different NP ratios, and the battery liquid injection coefficient is smaller than 3g/Ah; the electrolyte adopts non-aqueous electrolyte.
2. The high first efficiency sodium ion battery of claim 1, wherein the active material of the positive electrode is selected from at least one of Na4Fe3(PO4)2(P2O7)、Na4Fe3-x Mnx(PO4)2(P2O7)、Na4Mn3(PO4)2(P2O7) and Na 3MnTi(PO4)3, wherein 0 < X < 3;
the active material of the negative electrode is at least one selected from NaTi 2(PO4)3 and Na 3MnTi(PO4)3.
3. The high first efficiency sodium ion battery of claim 1, wherein the battery NP ratio is free of design, and wherein the battery NP ratio is in the range of 0.8 to 1.2.
4. The high first-efficiency sodium ion battery according to claim 1, wherein the concentration of the electrolyte is 0.2 to 1mol/kg when the NP ratio of the battery is 0.8 to 1.0.
5. The high first efficiency sodium ion battery of claim 1, wherein the electrolyte concentration is 1 to 5mol/kg when the battery NP ratio is 1.0 to 1.2.
6. The high first efficiency sodium ion battery of claim 1, wherein the charge-discharge potential of the negative electrode is at 2.1V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410082407.7A CN117954626A (en) | 2024-01-19 | 2024-01-19 | High first effect sodium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410082407.7A CN117954626A (en) | 2024-01-19 | 2024-01-19 | High first effect sodium ion battery |
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| Publication Number | Publication Date |
|---|---|
| CN117954626A true CN117954626A (en) | 2024-04-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410082407.7A Pending CN117954626A (en) | 2024-01-19 | 2024-01-19 | High first effect sodium ion battery |
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| Country | Link |
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| CN (1) | CN117954626A (en) |
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- 2024-01-19 CN CN202410082407.7A patent/CN117954626A/en active Pending
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