CN105720247A - Preparation method of composite cathode material for lithium-sodium mixed ion battery - Google Patents
Preparation method of composite cathode material for lithium-sodium mixed ion battery Download PDFInfo
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Abstract
The invention relates to a preparation method of a composite cathode material for a lithium-sodium mixed ion battery. According to the method, a high-energy phosphate compound Na2ATP is adopted as a structure template; a sodium source, a phosphorus source and a carbon source are introduced; and a new composite material Li3V2(PO4)3/Na4FeO3/C60 is synthesized by a biological-chemical synthesis method, a freeze-drying technology and a carbon thermal reduction technology. The material has good electrochemical properties, has the characteristics of over-discharge self-protection and high-rate circulating specific capacity self-increase, and can be applied to the lithium-sodium mixed ion battery as the cathode material.
Description
Technical field
The present invention relates to a kind of there is good electrical chemical property and overdischarge self-shield and high-multiplying power discharge specific capacity from increasing performance
Phosphoric acid vanadium lithium/sodium ferrite/carbon 60 (Li3V2(PO4)3/Na4FeO3/C60) preparation method of lithium-sodium hybrid ionic cell positive material,
Belong to lithium-sodium hybrid ionic cell positive material technical field.
Background technology
Phosphoric acid vanadium lithium is NASICON structure, has monocline and two kinds of crystal formations of rhombus.Phosphoric acid vanadium lithium structure by vanadium oxygen octahedra and
Phosphoric acid tetrahedron shares the summit link altogether of an oxygen atom and forms, and the connected mode of two kinds of structures and the position of lithium ion also exist district
Not.In rhombus vanadium phosphate crystalline lithium structure, lithium ion occupies two different positions: when the lithium ion content in structure is relatively low,
Lithium ion occupies tetrahedron space A (1)；When lithium ion content is higher, lithium ion can optionally occupy A (1) or
Other three octahedra spaces.The 3d space structure opened wide can make lithium ion freely move between A (1) and A (2) position
Move.In monoclinic lithium vanadium phosphate structure, each vanadium oxygen octahedra is surrounded by six phosphorus oxygen tetrahedrons, and each phosphorus oxygen tetrahedron is by four
Vanadium oxygen octahedra surrounds, and this configuration forms a tridimensional network with A2B3 as unit, and lithium is embedded in the hole of framework.
Three PO are included at phosphoric acid vanadium lithium molecule4Tetrahedron, two VO6Octahedron and three lithium ions, wherein Li (1) occupies one
Individual tetrahedral interstice, Li (2) and Li (3) are in occupation of the tetrahedral interstice of serious distortion in framework, because this tetrahedron has one
Longer Li-O key.
Sodium ferrite (Na4FeO3) there is good heat stability, its solid phase synthesis temperature is 450 DEG C, less than the shape of phosphoric acid vanadium lithium
Become temperature.Carry out being combined by sodium ferrite and phosphoric acid vanadium lithium and can improve cell positive material heat stability in charge and discharge process.By
In Fe2+Existence make battery material Fe in charge and discharge process2+/Fe3+Redox couple generation redox reaction, therefore ferrum
Acid sodium also has certain charge/discharge capacity.
M.S.KLochko etc. (Low Temp.Phys., 2015,41,488) have reported C60Molecular structure due to its uniqueness
With quantum size effect and there is the advantage that electro-chemical activity is high and electron conduction is good.C60As a kind of crystal material with carbon element, due to
The existence of π key and there is good electron conduction, can be effectively by improving cell positive material in battery charge and discharge process
Electric conductivity and reduce the activation polarization of electrode.C.X.Cui etc. (J.Phys.Chem.A, 2015,119,3098) demonstrate gold
Belong to ion and can embed C60Nanocages, C60Nanocages can be opened and carry out the storage of lithium ion and sodium ion, carries further
The charging and discharging capacity of high material.
Although lithium ion battery has been commercially produced at present, but there is also cost height, must have special protection circuit,
To prevent from overcharging or crossing deficiencies such as putting；And the sodium-ion battery just risen low cost, safety compared with lithium ion battery is good, but
There is the shortcoming that reversible capacity is low, energy density is low, cyclical stability is poor.According to the market demand of secondary cell, it is badly in need of research and development
New positive electrode, improves the chemical property of phosphoric acid vanadium lithium further, reduces cost, improves material peace in use
Quan Xing, thus meet the new energy field needs to secondary battery material.
Summary of the invention
The deficiency existed for existing lithium ion battery material and sodium-ion battery material, the present invention provides one to have good electrification
Learn performance and overdischarge self-shield and high rate capability from the lithium-sodium hybrid ionic battery composite anode material increased
Li3V2(PO4)3/Na4FeO3/C60Preparation method.The present invention is to use immature earthen sites, by lyophilization and carbon thermal reduction
Technology will contain lithium ion phase and be combined with sodium ion phase and carbon 60, and the composite of synthesis can be as lithium-sodium hybrid ionic electricity
The positive electrode in pond.
Term explanation
Lithium-sodium hybrid ionic battery: on electrode, existing lithium ion deintercalation has again the battery of sodium ion deintercalation in charge and discharge process.
High-energy phosphate compound: refer to that during hydrolysis, the energy of release is at the phosphate cpd of more than 20.92kJ/moL.
Technical scheme is as follows:
A kind of lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including step such as
Under:
(1) high-energy phosphate compound aqueous solution is cultivated under the conditions of 30～50 DEG C；
(2) according to mol ratio Fe3+:PO4 3-=1:(1/2～2), source of iron solution is joined in the solution obtained by step (1),
Regulation pH=2～4, stirs, and still aging rear centrifugation obtains precipitate；
(3) in the precipitate that step (2) obtains, deionized water is added, according to mol ratio Fe:V=1:(1/3～3), in stirring
Under the conditions of add vanadium source, stir, obtain turbid liquid；
(4) turbid liquid cold drying step (3) obtained, obtains powder；According to mol ratio Fe:Li=1:(1/4～2) to powder
Middle addition lithium source, according to mol ratio Fe:C=(5～2): 1 adds carbon source, mixing and ball milling, obtains presoma；
(5) presoma step (4) prepared under nitrogen protection, is warming up to 600～800 DEG C and carries out heat treatment, heat treatment
Natural cooling after completing, obtains lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60。
According to the invention it is preferred to, the high-energy phosphate compound described in step (1) is adenosine triphosphate disodium salt (Na2ATP),
The concentration of high-energy phosphate compound aqueous solution is 0.017moL/L；
Preferably, incubation time is 20～60min.Na2ATP introduces sodium ion, it is provided that phosphorus source, carbon source, and as nanometer
The template of self-assembled structures.
According to the invention it is preferred to, the source of iron described in step (2) is iron chloride, and the concentration of source of iron solution is 0.496mol/L；
Preferably, described Fe3+:PO4 3-Mol ratio be 1:1；
Preferably, the regulation raw materials used HCl for 1mol/L of pH.Regulation pH=2～4, obtains cream colour color cloud after stirring
Liquid, still aging rear being centrifuged obtains beige precipitate thing.
According to the invention it is preferred to, the Fe:V mol ratio described in step (3) is 1:1, and vanadium source is ammonium metavanadate.Add
Vanadium source, stirs, and obtains the turbid liquid of yellow.
According to the invention it is preferred to, the lithium source described in step (4) is lithium carbonate, and described carbon source is glucose；
Preferably, Fe:Li mol ratio=1:1, Fe:C mol ratio=4:1；
Preferably, cold drying mode is lyophilization, and further preferred drying condition is-50 DEG C, 28Pa；During cold drying
Between be 12h, the mixing and ball milling time is 2h.Add vanadium source, stir, obtain cadmium yellow color cloud liquid, after cold drying, obtain foresythia
Powder.
According to the invention it is preferred to, in step (5), heat treatment temperature is 700 DEG C, and heat treatment time is 8h.
The Li that step of the present invention (6) obtains3V2(PO4)3/Na4FeO3/C60Positive electrode as hybrid ionic battery is applied,
Concrete application process is as follows:
(1) by Li3V2(PO4)3/Na4FeO3/C60It is fully ground with conductive agent and binding agent after mixing, adds N-crassitude
Ketone solvent, obtains after stirring precoating refined serosity；
(2) above-mentioned precoating is refined serosity and coat on aluminium foil, then will i.e. obtain lithium-sodium hybrid ionic after electrode slice dried
Anode electrode slice, gained lithium-sodium hybrid ionic anode electrode slice is used for button-type battery lithium-sodium hybrid ionic battery.
Lithium prepared by the inventive method-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60, in charge and discharge
Piezoelectric voltage be the first discharge specific capacity under 2.5～4.2V and 10.0C multiplying powers be 78.5mAh/g, circulate the electric discharge after 300 times
Specific capacity is 98.4mAh/g (pure phosphoric acid vanadium lithium is generally about 80mAh/g).Fill under 2.5～4.2V and 1.0C multiplying powers
After electricity, overdischarge more than 90% battery remains to normal circulation.
Beneficial effects of the present invention is as follows:
The present invention uses high-energy phosphate compound Na2ATP is stay in place form and introduces sodium source, phosphorus source and carbon source, by biological-change
Learn synthetic method, Freeze Drying Technique and carbon thermal reduction technology and synthesize a kind of new composite L i3V2(PO4)3/Na4FeO3/C60,
Not only there is good chemical property, and there is overdischarge self-shield and high rate cyclic specific capacity from the characteristic increased, can
As positive electrode for lithium-sodium hybrid ionic battery.
Accompanying drawing explanation
Fig. 1 is the lithium-sodium hybrid ionic battery composite anode material Li of the embodiment of the present invention 1 synthesis3V2(PO4)3/Na4FeO3/C60
XRD figure, wherein vertical coordinate is diffracted intensity, and abscissa is angle of diffraction (2 θ).
Fig. 2 is the lithium-sodium hybrid ionic battery composite anode material Li of the embodiment of the present invention 1 synthesis3V2(PO4)3/Na4FeO3/C60
Electrochemistry cycle performance figure.
Detailed description of the invention
Below by specific embodiment and combine accompanying drawing the present invention will be further described, but it is not limited to this.
Raw materials used in embodiment it is convenient source.
Embodiment 1
A kind of lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including step such as
Under:
(1) by the Na of 200mL 0.017mol/L2ATP aqueous solution cultivates 30min under the conditions of 40 DEG C；
(2) according to mol ratio Fe3+:PO4 3-=1:1 is by the FeCl of 20mL 0.496mol/L3Solution is slowly added into above-mentioned molten
In liquid, regulate pH=3 with the HCl of 1mol/L, stir 2h, it is thus achieved that cream colour color cloud liquid, be centrifuged after still aging 4h and obtain rice
Yellow mercury oxide；
(3) in beige precipitate thing, then add deionized water be diluted to turbid liquid and be settled to 200mL, according to mol ratio
Fe:V=1:1 stirs 2h after adding 1.1688g ammonium metavanadate and obtains cadmium yellow color cloud liquid；
(4) by cadmium yellow color cloud liquid in-50 DEG C, under the conditions of 28Pa, lyophilization becomes bright-yellow powder；According to mol ratio Fe:Li=1:1
In bright-yellow powder, add 0.3664g lithium carbonate and 0.0744g glucose, mixing and ball milling 2h with Fe:C=4:1 respectively, prepare
Presoma；
(5) by prepared presoma under nitrogen protection, it is warming up to 700 DEG C of heat treatment 8h, after natural cooling, prepares
Li3V2(PO4)3/Na4FeO3/C60Composite positive pole, its XRD figure is as shown in Figure 1.
Electrochemical property test
Lithium-sodium hybrid ionic battery composite anode material Li that this embodiment is prepared3V2(PO4)3/Na4FeO3/C60As lithium-sodium
Hybrid ionic battery, uses rubbing method to prepare electrode.By lithium-sodium hybrid ionic battery composite anode material
Li3V2(PO4)3/Na4FeO3/C60, acetylene black and Kynoar (PVDF) be fully ground mixing by the mass ratio of 80:10:10,
Obtain precoating refined serosity after addition N-Methyl pyrrolidone stirring solvent is uniform；Above-mentioned precoating is refined serosity and coats aluminium foil
On, through 60 DEG C of dry 6h and 120 DEG C of vacuum drying 12h, after natural cooling, utilize sheet-punching machine to be cut into the disk of diameter 15cm,
I.e. make lithium-sodium hybrid ionic anode electrode slice.
Assemble successively according to the order of anode cover-electrode slice-electrolyte-barrier film-electrolyte-lithium sheet-pad-spring leaf-negative electrode casing, then
Utilize sealing machine by cell sealing, can be prepared by CR2032 type button half-cell.Finally high in A713-2008S-3TGF-A type
Precision discharge and recharge instrument carries out constant current charge-discharge test to battery.
Above-mentioned synthetic material is under charging/discharging voltage is 2.5～4.2V and 10.0C multiplying powers, and first discharge specific capacity is 78.5mAh/g,
Circulating the specific discharge capacity after 300 times is 98.4mAh/g, and its electrochemistry cycle performance is as shown in Figure 2.
Embodiment 2
A kind of lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including step such as
Under:
(1) by the Na of 200mL 0.017mol/L2ATP aqueous solution cultivates 30min under the conditions of 50 DEG C；
(2) according to mol ratio Fe3+:PO4 3-=1:1 is by the FeCl of 20mL 0.496mol/L3Solution is slowly added into above-mentioned molten
In liquid, regulate pH=2 with the HCl of 1mol/L, stir 2h, it is thus achieved that cream colour color cloud liquid, be centrifuged after still aging 4h and obtain rice
Yellow mercury oxide；
(3) in beige precipitate thing, then add deionized water be diluted to turbid liquid and be settled to 200mL, according to mol ratio
Fe:V=1:1/2 stirs 2h after adding 0.5844g ammonium metavanadate and obtains cadmium yellow color cloud liquid；
(4) by cadmium yellow color cloud liquid in-50 DEG C, under the conditions of 28Pa, lyophilization becomes bright-yellow powder；According to mol ratio Fe:Li=1:1
In bright-yellow powder, 0.3664g lithium carbonate and 0.0744g glucose is added respectively, before mixing and ball milling 2h prepares with Fe:C=4:1
Drive body；
(5) by prepared presoma under nitrogen protection, it is warming up to 600 DEG C of heat treatment 8h, after natural cooling, prepares
Li3V2(PO4)3/Na4FeO3/C60Composite positive pole.
Under charging/discharging voltage is 2.5～4.2V and 10.0C multiplying powers, the first discharge specific capacity of synthetic material is 64.8mAh/g,
Specific discharge capacity after charge and discharge cycles 300 times is 43.5mAh/g.
Embodiment 3
A kind of lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including step such as
Under:
(1) by the Na of 200mL 0.017mol/L2ATP aqueous solution cultivates 30min under the conditions of 30 DEG C；
(2) according to mol ratio Fe3+:PO4 3-=1:1 is by the FeCl of 20mL 0.496mol/L3Solution is slowly added into above-mentioned molten
In liquid, regulate pH=4 with the HCl of 1mol/L, stir 2h, it is thus achieved that cream colour color cloud liquid, be centrifuged after still aging 4h and obtain rice
Yellow mercury oxide；
(3) in beige precipitate thing, then add deionized water be diluted to turbid liquid and be settled to 200mL, according to mol ratio
Fe:V=1:2 stirs 2h after adding 2.3376g ammonium metavanadate and obtains cadmium yellow color cloud liquid；
(4) by cadmium yellow color cloud liquid in-50 DEG C, under the conditions of 28Pa, lyophilization becomes bright-yellow powder；According to mol ratio Fe:Li=1:1
In bright-yellow powder, 0.3664g lithium carbonate and 0.0744g glucose is added respectively, before mixing and ball milling 2h prepares with Fe:C=4:1
Drive body；
(5) by prepared presoma under nitrogen protection, it is warming up to 800 DEG C of heat treatment 8h, after natural cooling, prepares
Li3V2(PO4)3/Na4FeO3/C60Composite positive pole.
Under charging/discharging voltage is 2.5～4.2V and 10.0C multiplying powers, the first discharge specific capacity of synthetic material is 76.3mAh/g,
Specific discharge capacity after charge and discharge cycles 300 times is 67.5mAh/g.
Embodiment 4
A kind of lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including step such as
Under:
(1) by the Na of 200mL 0.017mol/L2ATP aqueous solution cultivates 30min under the conditions of 30 DEG C；
(2) according to mol ratio Fe3+:PO4 3-=1:1/2 is by the FeCl of 40mL 0.496mol/L3Solution is slowly added into above-mentioned
In solution, regulate pH=4 with the HCl of 1mol/L, stir 2h, it is thus achieved that cream colour color cloud liquid, be centrifuged after still aging 4h and obtain
Beige precipitate thing；
(3) in beige precipitate thing, then add deionized water be diluted to turbid liquid and be settled to 200mL, according to mol ratio
Fe:V=1:2 stirs 2h after adding 2.3376g ammonium metavanadate and obtains cadmium yellow color cloud liquid；
(4) by cadmium yellow color cloud liquid in-50 DEG C, under the conditions of 28Pa, lyophilization becomes bright-yellow powder；According to mol ratio Fe:Li=1:1/4
In bright-yellow powder, 0.0916g lithium carbonate and 0.0595g glucose is added respectively, before mixing and ball milling 2h prepares with Fe:C=5:1
Drive body；
(5) by prepared presoma under nitrogen protection, it is warming up to 800 DEG C of heat treatment 8h, after natural cooling, prepares
Li3V2(PO4)3/Na4FeO3/C60Composite positive pole.
Embodiment 5
A kind of lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including step such as
Under:
(1) by the Na of 200mL 0.017mol/L2ATP aqueous solution cultivates 30min under the conditions of 30 DEG C；
(2) according to mol ratio Fe3+:PO4 3-=1:2 is by the FeCl of 10mL 0.496mol/L3Solution is slowly added into above-mentioned molten
In liquid, regulate pH=4 with the HCl of 1mol/L, stir 2h, it is thus achieved that cream colour color cloud liquid, be centrifuged after still aging 4h and obtain rice
Yellow mercury oxide；
(3) in beige precipitate thing, then add deionized water be diluted to turbid liquid and be settled to 200mL, according to mol ratio
Fe:V=1:2 stirs 2h after adding 2.3376g ammonium metavanadate and obtains cadmium yellow color cloud liquid；
(4) by cadmium yellow color cloud liquid in-50 DEG C, under the conditions of 28Pa, lyophilization becomes bright-yellow powder；According to mol ratio Fe:Li=1:2
In bright-yellow powder, 0.7328g lithium carbonate and 0.1488g glucose is added respectively, before mixing and ball milling 2h prepares with Fe:C=2:1
Drive body；
(5) by prepared presoma under nitrogen protection, it is warming up to 800 DEG C of heat treatment 8h, after natural cooling, prepares
Li3V2(PO4)3/Na4FeO3/C60Composite positive pole.
Claims (10)
1. lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including step
As follows:
(1) high-energy phosphate compound aqueous solution is cultivated under the conditions of 30～50 DEG C；
(2) according to mol ratio Fe3+:PO4 3-=1:(1/2～2), source of iron solution is joined in the solution obtained by step (1),
Regulation pH=2～4, stirs, and still aging rear centrifugation obtains precipitate；
(3) in the precipitate that step (2) obtains, deionized water is added, according to mol ratio Fe:V=1:(1/3～3), in stirring
Under the conditions of add vanadium source, stir, obtain turbid liquid；
(4) turbid liquid cold drying step (3) obtained, obtains powder；According to mol ratio Fe:Li=1:(1/4～2) to powder
Middle addition lithium source, according to mol ratio Fe:C=(5～2): 1 adds carbon source, mixing and ball milling, obtains presoma；
(5) presoma step (4) prepared under nitrogen protection, is warming up to 600～800 DEG C and carries out heat treatment, heat treatment
Natural cooling after completing, obtains lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60。
Lithium the most according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60System
Preparation Method, it is characterised in that the high-energy phosphate compound described in step (1) is adenosine triphosphate disodium salt (Na2ATP)。
Lithium the most according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60System
Preparation Method, it is characterised in that the concentration of the high-energy phosphate compound aqueous solution described in step (1) is 0.017moL/L.
Lithium the most according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60System
Preparation Method, it is characterised in that the source of iron described in step (2) is iron chloride, the concentration of source of iron solution is 0.496mol/L.
Lithium the most according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60System
Preparation Method, it is characterised in that the Fe described in step (2)3+:PO4 3-Mol ratio be 1:1.
Lithium the most according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60System
Preparation Method, it is characterised in that the Fe:V mol ratio described in step (3) is 1:1, vanadium source is ammonium metavanadate.
Lithium the most according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60System
Preparation Method, it is characterised in that the lithium source described in step (4) is lithium carbonate, described carbon source is glucose.
Lithium the most according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60System
Preparation Method, it is characterised in that Fe:Li mol ratio=1:1, Fe:C mol ratio=4:1 in step (4).
Lithium the most according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60System
Preparation Method, it is characterised in that in step (4), cold drying mode is lyophilization；Preferably drying condition is-50 DEG C, 28Pa.
Lithium the most according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60System
Preparation Method, it is characterised in that in step (5), heat treatment temperature is 700 DEG C, heat treatment time is 8h.
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Cited By (5)
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| CN109192982A (en) * | 2018-09-05 | 2019-01-11 | 四川大学 | The synthetic method of sulfuric acid ferrisodium positive electrode |
| CN113193166A (en) * | 2021-04-28 | 2021-07-30 | 珠海冠宇电池股份有限公司 | Positive plate, battery core and battery |
| 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 |
| CN114583136A (en) * | 2022-03-16 | 2022-06-03 | 安徽云储盈鑫有限责任公司 | Preparation method of high-performance lithium/sodium ion battery and battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108598418A (en) * | 2018-04-24 | 2018-09-28 | 齐鲁工业大学 | A kind of unformed NaVOPO of anode material of lithium-ion battery4/ C and the preparation method and application thereof |
| CN108598418B (en) * | 2018-04-24 | 2021-01-26 | 齐鲁工业大学 | Amorphous NaVOPO (sodium VOPO) as negative electrode material of sodium ion battery4/C and preparation method and application thereof |
| CN109192982A (en) * | 2018-09-05 | 2019-01-11 | 四川大学 | The synthetic method of sulfuric acid ferrisodium positive electrode |
| CN109192982B (en) * | 2018-09-05 | 2021-08-24 | 四川大学 | Method for synthesizing sodium ferric sulfate anode material |
| CN113193166A (en) * | 2021-04-28 | 2021-07-30 | 珠海冠宇电池股份有限公司 | Positive plate, battery core and battery |
| 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 |
| CN114583136A (en) * | 2022-03-16 | 2022-06-03 | 安徽云储盈鑫有限责任公司 | Preparation method of high-performance lithium/sodium ion battery and battery |
| CN114583136B (en) * | 2022-03-16 | 2024-01-26 | 安徽云储盈鑫有限责任公司 | Preparation method of high-performance lithium/sodium ion battery and battery |
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