CN113823856A - Formation method and preparation method of sodium ion battery and sodium ion battery - Google Patents
Formation method and preparation method of sodium ion battery and sodium ion battery Download PDFInfo
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- CN113823856A CN113823856A CN202111118662.5A CN202111118662A CN113823856A CN 113823856 A CN113823856 A CN 113823856A CN 202111118662 A CN202111118662 A CN 202111118662A CN 113823856 A CN113823856 A CN 113823856A
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 105
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims description 52
- 239000000654 additive Substances 0.000 claims description 36
- 239000003792 electrolyte Substances 0.000 claims description 35
- 230000000996 additive effect Effects 0.000 claims description 32
- 229910052708 sodium Inorganic materials 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 20
- 159000000000 sodium salts Chemical class 0.000 claims description 18
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical group FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 17
- 239000007774 positive electrode material Substances 0.000 claims description 16
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims description 13
- JKUAHMKHSDOYKZ-UHFFFAOYSA-N FC(C(F)(F)F)(OP1N=PN=P[N]1)F Chemical compound FC(C(F)(F)F)(OP1N=PN=P[N]1)F JKUAHMKHSDOYKZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- QGUHMPOHPMAXBY-UHFFFAOYSA-N FC(C(OP1N=PN=P[N]1)=C(C(F)=C1F)F)=C1F Chemical compound FC(C(OP1N=PN=P[N]1)=C(C(F)=C1F)F)=C1F QGUHMPOHPMAXBY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021201 NaFSI Inorganic materials 0.000 claims description 3
- 229910019398 NaPF6 Inorganic materials 0.000 claims description 3
- HRSNTDPZHQCOGI-UHFFFAOYSA-N carbonyl difluoride ethene Chemical compound C=C.C(=O)(F)F HRSNTDPZHQCOGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 3
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 5
- 230000002427 irreversible effect Effects 0.000 abstract 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 description 30
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 26
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 26
- -1 NaTFSI sodium salt Chemical class 0.000 description 13
- 239000008151 electrolyte solution Substances 0.000 description 13
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 229910021385 hard carbon Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 239000006245 Carbon black Super-P Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 229960003351 prussian blue Drugs 0.000 description 4
- 239000013225 prussian blue Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000009517 secondary packaging Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910018434 Mn0.5O2 Inorganic materials 0.000 description 1
- 229910014515 Na0.6MnO2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
-
- 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
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a formation method and a preparation method of a sodium ion battery and the sodium ion battery, comprising the following steps: the method comprises the steps that a sodium ion battery cell is placed in a formation cabinet to be charged, and after the charging voltage reaches a cut-off voltage, the charging is continued until the formation upper limit voltage is reached, wherein the formation upper limit voltage is larger than the cut-off voltage; then discharging to the lower limit voltage to finish the formation of the sodium-ion battery. Compared with the prior art, the sodium ion battery formation method provided by the invention comprises two-step charging formation, after the formation is finished on the basis of the cut-off voltage, the voltage is continuously increased to the formation upper limit voltage for formation, so that surplus sodium ions in the anode material can be removed, the first charging capacity is further improved, the irreversible capacity loss of the first circle is made up, the first charging efficiency is improved, and the first charging efficiency can be improved by 1-10%.
Description
Technical Field
The invention relates to the field of sodium ion batteries, in particular to a formation method and a preparation method of a sodium ion battery and the sodium ion battery.
Background
The sodium ion battery has wide application prospect in the field of energy storage due to the advantages of rich sodium resource, low cost, good safety performance and the like, has a similar working principle to the lithium ion battery, and realizes the storage and release of energy by utilizing the reversible embedding and releasing of sodium ions between a positive electrode and a negative electrode. However, the sodium ion battery consumes a portion of sodium ions during the first charge and discharge due to the formation of a solid electrolyte film (SEI film) at the negative electrode, thereby causing the loss of sodium as a positive electrode material, and thus reducing the energy density of the battery.
In order to improve the energy density of the sodium ion battery, the currently reported methods mainly include: (1) supplementing sodium to the negative electrode; (2) supplementing sodium with a solvent; (3) and supplementing sodium to the positive electrode. However, the above methods all require introducing an external sodium source into the sodium ion battery system, which is cumbersome in process, and the external sodium source such as metallic sodium poses safety risks.
In view of the above, it is necessary to provide a technical solution to the above problems.
Disclosure of Invention
One of the objects of the present invention is: the formation method of the sodium ion battery is provided to solve the problems of low first cycle efficiency and low first discharge capacity of the conventional sodium ion battery, and the formation method can fully remove the surplus sodium ions in the positive electrode material so as to make up the irreversible capacity loss of the first-cycle sodium ions.
In order to achieve the purpose, the invention adopts the following technical scheme:
a formation method of a sodium-ion battery comprises the following steps: the method comprises the steps that a sodium ion battery cell is placed in a formation cabinet to be charged, and after the charging voltage reaches a cut-off voltage, the charging is continued until the formation upper limit voltage is reached, wherein the formation upper limit voltage is larger than the cut-off voltage; then discharging to the lower limit voltage to finish the formation of the sodium-ion battery.
Preferably, the voltage of the positive electrode of the sodium-ion battery to sodium under the cut-off voltage is V1, the voltage of the positive electrode of the sodium-ion battery to sodium under the formation upper limit voltage is V2, and V2-V1 are more than or equal to 0.45V.
Preferably, the positive electrode material adopted by the sodium ion battery cell is NaxMM’(CN)6When the material is MM', is at least one of Fe, Co, Mn and Ni, x is more than or equal to 1, V1 is 3.6-4.0V, and V2 is 4.1-4.8V.
Preferably, the positive electrode material adopted by the sodium ion battery cell is NaxMO2When M is at least one of Ni, Co, Mn, Fe, Cu, Ti and V, x is more than 0 and less than or equal to 1; the V1 is 3.8-4.3V, and the V2 is 4.1-4.8V.
Preferably, the charging current is 0.01-1C.
Another object of the present invention is to provide a method for manufacturing a sodium ion battery, including the method for forming a sodium ion battery according to any one of the above aspects.
The invention also aims to provide a sodium-ion battery prepared by the preparation method of the sodium-ion battery.
Preferably, the electrolyte used by the sodium ion battery comprises a sodium salt, a carbonate solvent and an additive.
Preferably, the sodium salt is NaPF6、NaClO4、NaBF4、NaFSI、NaTFSI、NaSO3CF3And Na (CH)3)C6H4SO3The concentration of the sodium salt is more than or equal to 1.2 mol/L.
Preferably, the additive comprises a first additive and a second additive, the first additive is fluoroethylene carbonate or ethylene difluorocarbonate, and the second additive is at least one of fluorocyclotriphosphazene, hexachlorocyclotriphosphazene, pentafluoroethoxycyclotriphosphazene and pentafluorophenoxycyclotriphosphazene.
Preferably, the mass of the first additive is 1-5% of the total mass of the electrolyte, and the mass of the second additive is 2-10% of the total mass of the electrolyte.
The invention has the beneficial effects that:
1) the formation method of the sodium ion battery provided by the invention comprises two-step charging formation, and after the formation is finished on the basis of the cut-off voltage, the voltage is continuously increased to the formation upper limit voltage for formation, so that redundant sodium ions in the anode material can be removed, the first charging capacity is further improved, the irreversible capacity loss of the first circle is made up, the first charging efficiency is also improved, and the first charging efficiency can be improved by 1-10%.
2) Based on the instability brought by high-charging voltage formation, the sodium ion battery provided by the invention is provided with a high-voltage-resistant electrolyte system, so that when the surplus sodium ions in the cathode material are separated by using high-charging voltage, the problems of electrolyte decomposition and cathode transition metal dissolution caused by first-pass overcharge can be prevented, and the problem of cycle life attenuation caused by overcharge is prevented.
Drawings
Fig. 1 is a charge-discharge curve diagram of the first turn of example 1 and comparative example 1 of the present invention.
FIG. 2 is a graph showing the room-temperature cycle capacity retention rates of example 1 and comparative example 1 of the present invention.
Detailed Description
The invention provides a formation method of a sodium-ion battery, which comprises the following steps: the method comprises the steps that a sodium ion battery cell is placed in a formation cabinet to be charged, and after the charging voltage reaches a cut-off voltage, the charging is continued until the formation upper limit voltage is reached, wherein the formation upper limit voltage is larger than the cut-off voltage; then discharging to the lower limit voltage to finish the formation of the sodium-ion battery.
The cutoff voltage of the invention is different according to different anode materials and cathode materials adopted by the sodium ion battery cell, and the specific charged voltage is also different. The cut-off voltage refers to the difference between the positive electrode potential and the negative electrode potential, for example, when the positive electrode is made of Prussian blue material (Prussian blue vs. Na)+The voltage of/Na is 4.05V), the negative electrode is hard carbon (hard carbon vs. Na)+Na voltage of 0.05V), cut-off voltage of 4.0V to 4.05V-0.05V; for another example, when the positive electrode is a Prussian blue material (Prussian blue vs. Na)+The voltage of/Na was 4.05V), and the negative electrode was tin (Sb vs. Na)+Na voltage of 0.5V), the cut-off voltage is 3.55V-4.05V-0.5V. The formation upper limit voltage is a voltage after the cutoff voltage is continuously raised, and preferably, electricity is suppliedThe pressure is increased to the overcharge state of the battery, and the surplus sodium ions can be removed to a greater extent.
Preferably, the voltage of the positive electrode of the sodium-ion battery to sodium under the cut-off voltage is V1, the voltage of the positive electrode of the sodium-ion battery to sodium under the formation upper limit voltage is V2, and V2-V1 are more than or equal to 0.45V.
In some embodiments, the positive electrode material adopted by the sodium ion battery cell is NaxMM’(CN)6When the material is MM', is at least one of Fe, Co, Mn and Ni, x is more than or equal to 1, V1 is 3.6-4.0V, and V2 is 4.1-4.8V.
In some embodiments, the positive electrode material adopted by the sodium ion battery cell is NaxMO2When M is at least one of Ni, Co, Mn, Fe, Cu, Ti and V, x is more than 0 and less than or equal to 1; the V1 is 3.8-4.3V, and the V2 is 4.1-4.8V. The common layered oxide positive electrode can be Na0.66Fe0.5Mn0.5O2,、Na0.6MnO2。
Further, the charging current is 0.01-1C. Preferably, the charging current is mainly low current charging and is 0.01-0.3C, so that a sodium ion battery system can better generate a compact and stable SEI film, and a more stable system basis is provided for overcharge of subsequent voltage increase. More preferably, the charging current is 0.1C.
The invention provides a preparation method of a sodium-ion battery, which comprises the formation method of the sodium-ion battery.
The invention provides a sodium-ion battery prepared by the preparation method of the sodium-ion battery.
Further, the electrolyte used by the sodium ion battery comprises a sodium salt, a carbonate solvent and an additive. Wherein the carbonate solvent comprises a cyclic carbonate solvent and a chain carbonate solvent.
Further, the sodium salt is NaPF6、NaClO4、NaBF4、NaFSI、NaTFSI、NaSO3CF3And Na (CH)3)C6H4SO3At least one ofAnd the concentration of the sodium salt is more than or equal to 1.2 mol/L. Preferably, NaTFSI sodium salt is adopted, and a passivation layer containing F can be formed on the surface of the electrode by high-concentration NaTFSI which is more than 1.2mol/L, so that the voltage interval of the electrolyte and the stability of the material can be remarkably improved.
Further, the additive comprises a first additive and a second additive, wherein the first additive is fluoroethylene carbonate or ethylene difluorocarbonate, and the second additive is at least one of fluorocyclotriphosphazene, hexachlorocyclotriphosphazene, pentafluoroethoxycyclotriphosphazene and pentafluorophenoxycyclotriphosphazene. Preferably, fluoroethylene carbonate and fluorocyclotriphosphazene are used as additives, and the fluoroethylene carbonate and fluorocyclotriphosphazene have lower redox potential, so that a compact SEI (solid electrolyte interphase) film containing F can be preferentially formed on the surface of the positive electrode, the contact between the electrolyte and the electrode is reduced, the damage of the electrolyte to the positive electrode structure under high voltage is prevented, the stability of the formation of the sodium ion battery under high voltage is ensured, and the problem of the attenuation of the cycle life caused by overcharge is avoided.
Further, the mass of the first additive is 1-5% of the total mass of the electrolyte, and the mass of the second additive is 2-10% of the total mass of the electrolyte. Through multiple experiments and verification of the inventor, the quality of the two additives is controlled within the range, and the two additives can be better ensured to preferentially form a compact SEI film containing F on the surface of the positive electrode.
In order to make the technical solutions and advantages of the present invention clearer, the present invention and its advantages will be described in further detail below with reference to the following detailed description and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a sodium-ion battery comprises the following steps:
1) preparing a positive pole piece: mixing Na1.92Fe[Fe(CN)6]·0.08H2Mixing O, acetylene black, super-P and PVDF according to the mass ratio of 90:2.5:2.5:5, coating, drying and rolling to obtain the positive plate.
2) Preparing a negative pole piece: mixing hard carbon: super-P: and (3) mixing PVDF according to the mass ratio of 90:5:5, coating, drying and rolling to obtain the negative plate. The capacity ratio of the positive plate to the negative plate is 1: 1.2.
3) A diaphragm: a polyethylene separator.
4) Electrolyte solution: the volume ratio is 1:1 Propylene Carbonate (PC) Ethylene Carbonate (EC) as solvent, 1.2M NaPF as sodium salt6The additive used was 4% fluoroethylene carbonate (FEC) and 5% pentafluoroethoxycyclotriphosphazene (PFPN).
5) Assembling the battery: assembling the positive pole piece, the diaphragm and the negative pole piece into a bare cell in a winding mode, packaging the bare cell by using an aluminum-plastic film, and injecting electrolyte to obtain the sodium ion cell.
6) Formation of the battery: standing a sodium ion battery cell, then charging to 4.0V under the current of 0.1C (at the moment, the voltage of the positive electrode material to sodium is 4.05V, and the voltage of the negative electrode hard carbon to sodium is 0.05V), and then continuously charging to 4.5V with the current of 0.1C (at the moment, the voltage of the positive electrode material to sodium is 4.55V, and the voltage of the negative electrode hard carbon to sodium is 0.05V); then discharging to 1.5V by 0.2C current to finish the formation of the sodium ion battery.
7) And after formation, exhausting air for the sodium-ion battery, carrying out secondary packaging and grading to complete the preparation of the sodium-ion battery.
Example 2
The difference from example 1 is the arrangement of the electrolyte.
4) Electrolyte solution: the volume ratio is 1:1 Propylene Carbonate (PC) Ethylene Carbonate (EC) as solvent, 1.8M NaPF as sodium salt6The additive used was 4% fluoroethylene carbonate (FEC) and 5% pentafluoroethoxycyclotriphosphazene (PFPN).
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
The difference from example 1 is the arrangement of the electrolyte.
4) Electrolyte solution: the volume ratio is 1:1 Propylene Carbonate (PC) Ethylene Carbonate (EC) as solvent, 1.8M NaTFSI for the sodium salt and 4% fluoroethoxy cyclotriphosphazene (PFPN) and 5% fluoroethoxy cyclotriphosphazene (FEC) for the additive.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is the arrangement of the electrolyte.
4) Electrolyte solution: the volume ratio is 1:1 Propylene Carbonate (PC) Ethylene Carbonate (EC) as solvent, 1.8M NaTFSI for the sodium salt and 1% fluoroethoxy cyclotriphosphazene (PFPN) for the additive.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from example 1 is the arrangement of the electrolyte.
4) Electrolyte solution: the volume ratio is 1:1 Propylene Carbonate (PC) Ethylene Carbonate (EC) as solvent, 1.8M NaTFSI for the sodium salt and 2% fluoroethoxy cyclotriphosphazene (PFPN) and 3% fluoroethoxy cyclotriphosphazene (FEC) for the additive.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
A preparation method of a sodium-ion battery comprises the following steps:
1) preparing a positive pole piece: mixing Na (Ni)0.5Mn0.5)O2The positive plate is prepared by mixing acetylene black, super-P and PVDF according to the mass ratio of 90:2.5:2.5:5, coating, drying and rolling.
2) Preparing a negative pole piece: mixing hard carbon: super-P: and (3) mixing PVDF according to the mass ratio of 90:5:5, coating, drying and rolling to obtain the negative plate. The capacity ratio of the positive plate to the negative plate is 1: 1.2.
3) A diaphragm: a polyethylene separator.
4) Electrolyte solution: the volume ratio is 1:1 Propylene Carbonate (PC) Ethylene Carbonate (EC) as solvent, 1.8M NaTFSI for the sodium salt and 1% fluoroethoxy cyclotriphosphazene (PFPN) for the additive.
5) Assembling the battery: assembling the positive pole piece, the diaphragm and the negative pole piece into a bare cell in a winding mode, packaging the bare cell by using an aluminum-plastic film, and injecting electrolyte to obtain the sodium ion cell.
6) Formation of the battery: standing a sodium ion battery cell, then charging to 3.8V under the current of 0.1C (at the moment, the voltage of the positive electrode material to sodium is 3.85V, and the voltage of the negative electrode hard carbon to sodium is 0.05V), and then continuously charging to 4.5V with the current of 0.1C (at the moment, the voltage of the positive electrode material to sodium is 4.55V, and the voltage of the negative electrode hard carbon to sodium is 0.05V); then discharging to 1.5V by 0.2C current to finish the formation of the sodium ion battery.
7) And after formation, exhausting air for the sodium-ion battery, carrying out secondary packaging and grading to complete the preparation of the sodium-ion battery.
Example 7
The difference from example 6 is the arrangement of the electrolyte.
4) Electrolyte solution: the volume ratio is 1:1 Propylene Carbonate (PC) Ethylene Carbonate (EC) as solvent, 1.8M NaTFSI for the sodium salt and 2% fluoroethoxy cyclotriphosphazene (PFPN) and 3% fluoroethoxy cyclotriphosphazene (FEC) for the additive.
The rest is the same as embodiment 6, and the description is omitted here.
Example 8
The difference from example 6 is the arrangement of the electrolyte.
4) Electrolyte solution: the volume ratio is 1:1 Propylene Carbonate (PC) Ethylene Carbonate (EC) as solvent, 1.8M NaTFSI for the sodium salt and 4% fluoroethoxy cyclotriphosphazene (PFPN) and 5% fluoroethoxy cyclotriphosphazene (FEC) for the additive.
The rest is the same as embodiment 6, and the description is omitted here.
Example 9
The difference from example 6 is the arrangement of the electrolyte.
4) Electrolyte solution: the volume ratio is 1:1 Propylene Carbonate (PC) Ethylene Carbonate (EC) as solvent, 1.8M NaPF as sodium salt6The additive used was 4% fluoroethylene carbonate (FEC) and 5% pentafluoroethoxycyclotriphosphazene (PFPN).
The rest is the same as embodiment 6, and the description is omitted here.
Comparative example 1
The difference from example 1 is the formation process.
6) Formation of the battery: and (3) standing the sodium ion battery cell, then charging under the current of 0.1C until the voltage of the positive electrode material to sodium is 4.05V, and then discharging to 1.5V under the current of 0.2C to finish the formation of the sodium ion battery.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 2
The difference from example 6 is the formation process.
6) Formation of the battery: and (3) standing the sodium ion battery cell, then charging under the current of 0.1C until the voltage of the positive electrode material to sodium is 3.85V, and then discharging to 1.5V under the current of 0.2C to finish the formation of the sodium ion battery.
The rest is the same as embodiment 6, and the description is omitted here.
Comparative example 3
The difference from example 1 is the arrangement of the electrolyte.
4) Electrolyte solution: the volume ratio is 1:1 Propylene Carbonate (PC) Ethylene Carbonate (EC) as solvent, 1.2M NaPF as sodium salt6。
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 4
The difference from example 6 is the arrangement of the electrolyte.
4) Electrolyte solution: the volume ratio is 1:1 Propylene Carbonate (PC): Ethylene Carbonate (EC) as solvent and 1.8M NaTFSI as sodium salt.
The rest is the same as embodiment 6, and the description is omitted here.
Comparative example 5
Different from the embodiment 1, the method is provided with the electrolyte and the formation process.
4) Electrolyte solution: the volume ratio is 1:1 Propylene Carbonate (PC) Ethylene Carbonate (EC) as solvent, 1.2M NaPF as sodium salt6。
6) Formation of the battery: and (3) standing the sodium ion battery cell, then charging under the current of 0.1C until the voltage of the positive electrode material to sodium is 4.05V, and then discharging to 1.5V under the current of 0.2C to finish the formation of the sodium ion battery.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 6
Different from the embodiment 6 is the arrangement of the electrolyte and the formation process.
4) Electrolyte solution: the volume ratio is 1:1 Propylene Carbonate (PC): Ethylene Carbonate (EC) as solvent and 1.8M NaTFSI as sodium salt.
6) Formation of the battery: and (3) standing the sodium ion battery cell, then charging under the current of 0.1C until the voltage of the positive electrode material to sodium is 3.85V, and then discharging to 1.5V under the current of 0.2C to finish the formation of the sodium ion battery.
The rest is the same as embodiment 6, and the description is omitted here.
The sodium ion batteries obtained in the embodiments 1-9 and the comparative examples 1-6 are subjected to performance detection, and the detection results are shown in the following table 1 and figures 1-2.
TABLE 1
The test results show that the formation method provided by the invention effectively improves the first-cycle discharge capacity and the first-cycle efficiency of the sodium-ion battery, because the formation with proper high voltage can remove the surplus sodium ions in the sodium anode material, thereby effectively improving the first-cycle charge-discharge capacity and the first-cycle efficiency. Meanwhile, the high-voltage resistant electrolyte is matched with the high-voltage formation, so that the situations of electrolyte decomposition and positive electrode filtering metal dissolution caused by overcharge of the first loop can be ensured when the charge-discharge capacity and efficiency of the first loop are improved, and the subsequent circulation of the sodium-ion battery is ensured. As shown in FIGS. 1-2, the capacity retention rate of example 1 during the subsequent cycles was not inferior to that of comparative example 1.
In addition, as can be seen from the comparison between examples 1 and 6 and comparative examples 1 to 6, the high-voltage formation method provided by the invention is complementary to the voltage-resistant electrolyte, and when the high-voltage formation method and the voltage-resistant electrolyte are controlled, the improvement effect on the performance of the sodium-ion battery is better, which is probably because the voltage-resistant electrolyte can not only avoid the damage of the electrolyte to the anode structure when generating the SEI film containing F, but also can further promote the extraction of the surplus sodium ions in the anode material, so that the performance of the sodium-ion battery in the first and subsequent cycles is effectively improved.
In addition, as can be seen from the comparison between the embodiments 1 to 5 and the embodiments 6 to 9, the electrolyte composed of fluoroethylene carbonate (FEC) and pentafluoroethoxycyclotriphosphazene is added while high-concentration NaTFSI is used as a sodium salt, so that the matching degree of the electrolyte with high voltage formation is higher, and the performance of the sodium ion battery is more favorably improved.
In conclusion, the formation method and the sodium ion battery provided by the invention effectively solve the problems of low first cycle efficiency and low first discharge capacity of the conventional sodium ion battery, and meanwhile, the sodium ion battery can still keep better cycle performance in the subsequent normal-temperature cycle process, the cycle life of the sodium ion battery cannot be attenuated due to the first high-voltage formation, and the application scene of the sodium ion battery is greatly expanded.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A formation method of a sodium ion battery is characterized by comprising the following steps: the method comprises the steps that a sodium ion battery cell is placed in a formation cabinet to be charged, and after the charging voltage reaches a cut-off voltage, the charging is continued until the formation upper limit voltage is reached, wherein the formation upper limit voltage is larger than the cut-off voltage; then discharging to the lower limit voltage to finish the formation of the sodium-ion battery.
2. The method for forming the sodium-ion battery according to claim 1, wherein the positive electrode-to-sodium voltage of the sodium-ion battery at the cut-off voltage is V1, the positive electrode-to-sodium voltage of the sodium-ion battery at the upper limit of the formation voltage is V2, and V2-V1 are not less than 0.45V.
3. The method of claim 2, wherein the positive electrode material of the Na-ion battery cell is NaxMM’(CN)6When the material is MM', is at least one of Fe, Co, Mn and Ni, x is more than or equal to 1, V1 is 3.6-4.0V, and V2 is 4.1-4.8V.
4. The method of claim 2, wherein the positive electrode material of the Na-ion battery cell is NaxMO2When M is at least one of Ni, Co, Mn, Fe, Cu, Ti and V, x is more than 0 and less than or equal to 1; the V1 is 3.8-4.3V, and the V2 is 4.1-4.8V.
5. A method for manufacturing a sodium-ion battery, characterized by comprising the method for forming a sodium-ion battery according to any one of claims 1 to 4.
6. A sodium-ion battery prepared by the method for preparing a sodium-ion battery according to claim 5.
7. The sodium ion battery of claim 6, wherein the electrolyte used in the sodium ion battery comprises a sodium salt, a carbonate solvent, and an additive.
8. The sodium-ion battery of claim 7, wherein the sodium salt is NaPF6、NaClO4、NaBF4、NaFSI、NaTFSI、NaSO3CF3And Na (CH)3)C6H4SO3The concentration of the sodium salt is more than or equal to 1.2 mol/L.
9. The sodium ion battery of claim 7, wherein the additives comprise a first additive and a second additive, wherein the first additive is fluoroethylene carbonate or ethylene difluorocarbonate, and wherein the second additive is at least one of fluorocyclotriphosphazene, hexachlorocyclotriphosphazene, pentafluoroethoxycyclotriphosphazene, and pentafluorophenoxycyclotriphosphazene.
10. The sodium-ion battery according to claim 9, wherein the mass of the first additive is 1 to 5% of the total mass of the electrolyte, and the mass of the second additive is 2 to 10% of the total mass of the electrolyte.
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