CN108630896A - A kind of secondary battery negative pole and preparation method thereof and secondary cell - Google Patents
A kind of secondary battery negative pole and preparation method thereof and secondary cell Download PDFInfo
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- CN108630896A CN108630896A CN201710184320.0A CN201710184320A CN108630896A CN 108630896 A CN108630896 A CN 108630896A CN 201710184320 A CN201710184320 A CN 201710184320A CN 108630896 A CN108630896 A CN 108630896A
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- phosphate
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of secondary battery negative poles, including metal foil and the fine and close metal phosphate film in metal foil surface is set, metal foil is used as negative current collector and negative electrode active material simultaneously, the material of metal foil includes any one in aluminium, copper, iron, tin, zinc, nickel, manganese, lead, antimony, cadmium and bismuth, or the alloy containing at least one above-mentioned metallic element；The material of metal phosphate film includes one or more in aluminum phosphate, cupric phosphate, ferric phosphate, phosphoric acid tin, trbasic zinc phosphate, nickel phosphate, manganese phosphate, lead phosphate, phosphoric acid antimony, cadmium phosphate and bismuth phosphate.The metal phosphate film that metal foil surface of the present invention is provided with one layer of electronic isolation, lithium ion can migrate.Metal phosphate film plays the function of similar solid electrolyte film；The compatibility for improving cathode and electrolyte improves efficiency for charge-discharge, cycle performance of battery, high temperature performance and the security performance of battery.The present invention also provides the preparation methods of secondary battery negative pole and a kind of secondary cell.
Description
Technical field
The present invention relates to secondary cell fields, and in particular to a kind of secondary battery negative pole and preparation method thereof and secondary electricity
Pond.
Background technology
2016, Shenzhen Xianjin Technology Academe of Chinese Academy of Sciences Tang Yong Ping researcher and its team leavened dough in new and effective battery
Remarkable Progress On Electric Artificial traveling exhibition, achievement in research is in the top periodical of energy and material《Advanced Energy Materials》On
(DOI:10.1002/aenm.201502588) issue a completely new aluminium-graphite Dual-ion cell technology, the technical work
Principle is different from existing traditional lithium battery, and using cheap graphite as anode, using aluminium foil simultaneously as negative electrode active material with
Collector；Again in notable material periodical when August part《Advanced Materials》Upper (DOI:10.1002/
Adma.201603735 " high magnification, long circulating, high-energy density based on the porous aluminium foil cathode of carbon coating pair) have been delivered online
Ion battery ".Its research team is using aluminium foil as the negative plate of new and effective battery, this new and effective battery system battery
Specific energy density higher, cost it is lower.Therefore this new and effective battery has great application prospect.Its research team fills
Point recognize using aluminium foil be used as when cathode pole piece there are the problem of, and propose and aluminium foil be processed into the porous aluminium foil of carbon coating
Solve aluminium foil volume expansion and electrolyte compatibility issue.Its achievement in research show they provide solution be can be effective
Solve the problems, such as that aluminium foil exists as negative plate.
By way of coating carbon material in aluminium foil surface, although improving the compatibility of cathode and electrolyte, also deposit
The problem of electrolyte is easily decomposed to form solid electrolyte film and consumes electrolyte.And there is also processing works for its carbon painting method
Skill is complicated, the higher problem of processing cost.
Invention content
It is directed to the above problem, the present invention proposes a kind of by the metal phosphate fine and close in metal foil surface setting
Film can improve the efficiency for charge-discharge, cycle performance and security performance of battery.
First aspect present invention provides secondary battery negative pole, including metal foil and the cause in the metal foil surface is arranged
Close metal phosphate film, the metal foil are used as negative current collector and negative electrode active material, the material of the metal foil simultaneously
Including any one in aluminium, copper, iron, tin, zinc, nickel, manganese, lead, antimony, cadmium and bismuth, or contain at least one above-mentioned metallic element
Alloy；The material of the metal phosphate film includes aluminum phosphate, cupric phosphate, ferric phosphate, phosphoric acid tin, trbasic zinc phosphate, nickel phosphate, phosphorus
It is one or more in sour manganese, lead phosphate, phosphoric acid antimony, cadmium phosphate and bismuth phosphate.
Wherein, the source metal in the metal phosphate film is identical as the metallic element in the metal foil.
Wherein, it is 10nm-20 μm that the surface layer of the metal foil, which has three-dimensional porous structure, porous pore size,.
Wherein, the thickness on the surface layer is 1nm-10 μm, and the thickness ratio of the thickness on the surface layer and the metal foil is 1:
10-10000。
Wherein, the thickness of the metal phosphate film is 1nm-3 μm, the metal phosphate film thickness and the metal foil
Thickness ratio be 1:30-10000.
The secondary battery negative pole that first aspect present invention provides, metal foil surface is provided with one in the secondary battery negative pole
The metal phosphate film that layer electronic isolation, metal ion such as lithium ion can migrate.The metal phosphate film plays similar
The function of solid electrolyte film；The compatibility of cathode and electrolyte is improved, electrolyte decomposition is reduced, improves battery
Efficiency for charge-discharge, cycle performance of battery, high temperature performance, security performance.
Second aspect of the present invention provides a kind of preparation method of secondary battery negative pole, including：
Metal foil raw material are provided, by the metal foil raw material and the solution containing phosphate radical carry out chemical reaction or
Fine and close metal phosphate film is formed by way of deposition on metal foil raw material surface, secondary battery negative pole is made；
The secondary battery negative pole includes metal foil and is arranged the fine and close metal phosphate film in the metal foil surface,
The metal foil is used as negative current collector and negative electrode active material simultaneously, the material of the metal foil include aluminium, copper, iron, tin,
Any one in zinc, nickel, manganese, lead, antimony, cadmium and bismuth, or the alloy containing at least one above-mentioned metallic element；The metal phosphorus
The material of hydrochlorate film includes aluminum phosphate, cupric phosphate, ferric phosphate, phosphoric acid tin, trbasic zinc phosphate, nickel phosphate, manganese phosphate, lead phosphate, phosphoric acid
It is one or more in antimony, cadmium phosphate and bismuth phosphate.
Wherein, include by the operation that the metal foil raw material are chemically reacted with the solution containing phosphate radical：
The metal foil raw material are immersed in the solution containing phosphate radical, impregnate 1 at a temperature of 0 DEG C -80 DEG C
- 600 minutes minutes；After immersion, secondary battery negative pole is made in washing, drying.
Wherein, the solution containing phosphate radical include phosphoric acid solution, phosphate dihydrogen salt solution, dibasic alkaliine solution,
At least one of pyrophosphate solution, pyrophosphate solution, metaphosphoric acid solution and metaphosphate solution；It is described containing phosphate radical
The mass fraction of solute in solution is 5%-85%.
Wherein, the operation of the drying includes：Under the conditions of 40 DEG C -120 DEG C, dry -600 minutes 30 minutes.
Second aspect of the present invention provide preparation method it is simple to operation, cost is relatively low, can industrialized production, and be easy system
Obtain the secondary battery negative pole that homogeneity of product is high, structure is uniform, performance is stablized.
Third aspect present invention provides a kind of secondary cell, including anode, electrolyte, diaphragm and such as preceding claim
Cathode described in first aspect.
Wherein, the electrolyte includes electrolyte and solvent, and the electrolyte includes lithium salts, sodium salt, sylvite, magnesium salts and calcium
Salt it is one or more；In the electrolyte, a concentration of 0.1mol/L-10mol/L of the electrolyte.
The secondary cell that third aspect present invention provides, efficiency for charge-discharge, cycle performance, high rate performance, the height of battery
Warm nature energy and security performance are preferable.
To sum up, advantageous effect of the present invention includes the following aspects：
1, the present invention provides a kind of secondary battery negative pole, metal foil surface is provided with one layer in the secondary battery negative pole
The metal phosphate film that electronic isolation, metal ion can migrate.The metal phosphate film plays similar solid electrolyte
The function of film；The compatibility of cathode and electrolyte is improved, electrolyte decomposition is reduced, improves the charge and discharge effect of battery
Rate, cycle performance of battery, high temperature performance, security performance；
2, preparation method provided by the invention is simple to operation, and cost is relatively low, can industrialized production, and be easy obtained product
The secondary battery negative pole that consistency is high, structure is uniform, performance is stablized；
3, secondary cell provided by the invention, efficiency for charge-discharge, cycle performance, high rate performance, the high temperature performance of battery
And security performance is preferable.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) figure of normal aluminium foil；
Fig. 2 is the SEM figures of secondary battery negative pole made from the embodiment of the present invention 1；
Fig. 3 is the enlarged drawing of the SEM figures of secondary battery negative pole made from the embodiment of the present invention 1；
Fig. 4 is X-ray energy spectrum (EDS) figure of secondary battery cathode pole surface made from the embodiment of the present invention 1.
Specific implementation mode
As described below is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Embodiment of the present invention first aspect provides a kind of secondary battery negative pole, including metal foil and setting in the gold
Belong to the fine and close metal phosphate film on foil surface, the metal foil is used as negative current collector and negative electrode active material simultaneously, described
The material of metal foil includes any one in aluminium, copper, iron, tin, zinc, nickel, manganese, lead, antimony, cadmium and bismuth, or contains at least one
The alloy of above-mentioned metallic element；The material of the metal phosphate film includes aluminum phosphate, cupric phosphate, ferric phosphate, phosphoric acid tin, phosphoric acid
It is one or more in zinc, nickel phosphate, manganese phosphate, lead phosphate, phosphoric acid antimony, cadmium phosphate and bismuth phosphate.
In mode of the embodiment of the present invention, according to specific applicable cases, the metal phosphate film can be provided in institute
The side surface for stating metal foil, can also be provided in the whole surface of metal foil.When the secondary cell is half-cell
It waits, the metal phosphate film can be provided only on the surface close to diaphragm side in metal foil；When the secondary cell is complete
Battery or for commercial battery group when, the metal phosphate film can be arranged in the both sides of metal foil being oppositely arranged
Whole surface in metal foil is arranged in surface.It is understood that can be reserved with for the exposed of soldering polar ear in metal foil
Metal phosphate film will not be arranged in region, the region.
In mode of the embodiment of the present invention, the secondary cell can be that lithium rechargeable battery, the sodium ion of routine are secondary
The batteries such as battery, or Dual-ion cell.
When the porous aluminium foil of the prior art had not only been used as negative electrode active material but also had been used as collector, since aluminium foil activity is very high,
Aluminium foil surface can have one layer of fine and close oxide thin layer aluminium, and battery lithium ion in charging is anti-into line replacement with aluminium oxide first
It answers, the aluminium in the compact aluminum oxide thin layer of aluminium foil surface carries out alloying with lithium ion again, at the same time aluminium foil surface contact
Electrolyte can decompose to form solid electrolyte film.Due to generating volume expansion when lithium-aluminium alloy so that formation
Solid electrolyte film is destroyed, and electrolyte, which carries out being decomposed to form solid electrolyte film before solid electrolyte film makes up again, to be broken
Bad place.And as lithium-aluminium alloy constantly carries out on aluminium foil, the degree of aluminium foil volume expansion continues to increase, electrolyte
Decomposition also constantly carrying out；Aluminium foil volume-diminished when electric discharge, there is also a degree of destructions for solid electrolyte film.Therefore
Battery is in charge and discharge process, and especially electrolyte decomposition is serious during battery first charge-discharge, the efficiency for charge-discharge of battery
It is relatively low.
In embodiment of the present invention, metal phosphate film has electronic isolation, and metal ion is as lithium ion can be connected
Property, the metal phosphate film play the role of similar solid electrolyte film function and.The secondary battery negative pole both conducts
Negative electrode active material is used as negative current collector again.Since there are the electronics on surface when this secondary battery negative pole is as cathode
Insulating layer can improve the stability of electrolyte to avoid electrolyte is contacted with negative electrode active material and causes electrolyte decomposition；Electricity
Solve matter in metal ion or positive electrode active materials in metal ion such as lithium ion by after metal phosphate film layer with gold
Belong to foil material such as aluminium and form lithium-aluminium alloy and removal alloying, to realize battery charging and discharging.And metal phosphate is in metal foil
Host inorganic component part of the surface as solid electrolyte film well leads lithium performance since it has, advantageous to reduce solid electricity
Solve the impedance of plasma membrane.Additionally due to metal phosphate film is generated in metal foil surface, with very strong adhesive force, to gold
Belong to foil matrix and form good protection effect, improves battery cathode and electrolyte compatibility, improve the efficiency for charge-discharge of battery, follow
Ring stability and security performance.
In embodiment of the present invention, the material of the metal foil includes metal simple-substance or metal alloy, be specifically as follows aluminium,
Copper, iron, tin, zinc, nickel, manganese, lead, antimony, cadmium, bismuth, copper-tin alloy, mock silver, aluminum titanium alloy, ferro-tin alloy etc., wherein alloy
The ratio of middle each element is conventional selection.
In embodiment of the present invention, the source metal in the metal phosphate film and the metallic element phase in the metal foil
Together.Such as when metal foil is aluminium foil, metal phosphate film is just phosphoric acid aluminium film.When metal foil is copper foil, metal phosphate
Film is just phosphoric acid copper film.Source metal in metal phosphate film can be consistent with the metallic element in the metal foil.
In embodiment of the present invention, it is 10nm- that the surface layer of the metal foil, which has three-dimensional porous structure, porous pore size,
20μm.Optionally, porous pore size is 10nm-100nm.Optionally, porous pore size is 1 μm -20 μm.The table of metal foil
Layer has three-dimensional porous structure, increases metal ion such as lithium ion mobility channel, advantageous lithium ion is embedded and deviates from, to carry
The high rate performance of high battery.In addition, the volume expansion of metal foil negative plate in battery charge and discharge process is alleviated, it is advantageous to improve electricity
The cycle performance in pond.
In embodiment of the present invention, the thickness on the surface layer is 1nm-10 μm, and optionally, the thickness on the surface layer is 1nm-
100nm, optionally, the thickness on the surface layer is 1 μm -10 μm.Optionally, the thickness of the thickness on the surface layer and the metal foil
Than being 1:10-10000.Optionally, the thickness on the surface layer and the thickness ratio of the metal foil are 1:10-100.Optionally, institute
The thickness for stating surface layer and the thickness ratio of the metal foil are 1:1000-10000.
In embodiment of the present invention, the metal phosphate film is fitted closely with the surface layer to realize metal phosphorus as far as possible
Hydrochlorate film is tightly disposed in the surface on the surface layer.
In embodiment of the present invention, the thickness of the metal phosphate film is 1nm-3 μm；Optionally, metal phosphate film
Thickness be 1nm-100nm；Optionally, the thickness of metal phosphate film is 100nm-3 μm.Optionally, the metal phosphate
Film thickness and the thickness ratio of the metal foil are 1:30-10000.Optionally, the metal phosphate film thickness and the metal
The thickness ratio of foil is 1:30-100；Optionally, the metal phosphate film thickness and the thickness ratio of the metal foil are 1:100-
10000。
First aspect present invention provides a kind of secondary battery negative pole, and metal foil surface is arranged in the secondary battery negative pole
There is the metal phosphate film that one layer of electronic isolation, metal ion such as lithium ion can migrate.The metal phosphate film plays
The function of similar solid electrolyte film；The compatibility of cathode and electrolyte is improved, electrolyte decomposition is reduced, improves electricity
The efficiency for charge-discharge in pond, cycle performance of battery, high temperature performance, security performance.In addition, the present invention is for the first time to metal foil conduct
Negative electrode active material is also used as when current collector material is surface-treated simultaneously, grows based solid electrolyte membrane substance, passes through
This mode can expand the range of choice of electrolyte solvent, to favorably realize electricity by the selection of electrolyte solvent optimization
Pond comprehensive performance expands the application field of battery.
Embodiment of the present invention second aspect provides a kind of preparation method of secondary battery negative pole, including：
Metal foil raw material are provided, by the metal foil raw material and the solution containing phosphate radical carry out chemical reaction or
Fine and close metal phosphate film is formed by way of deposition on metal foil raw material surface, secondary battery negative pole is made；
The secondary battery negative pole includes metal foil and is arranged the fine and close metal phosphate film in the metal foil surface,
The metal foil is used as negative current collector and negative electrode active material simultaneously, the material of the metal foil include aluminium, copper, iron, tin,
Any one in zinc, nickel, manganese, lead, antimony, cadmium and bismuth, or the alloy containing at least one above-mentioned metallic element；The metal phosphorus
The material of hydrochlorate film includes aluminum phosphate, cupric phosphate, ferric phosphate, phosphoric acid tin, trbasic zinc phosphate, nickel phosphate, manganese phosphate, lead phosphate, phosphoric acid
It is one or more in antimony, cadmium phosphate and bismuth phosphate.
In mode of the embodiment of the present invention, according to specific applicable cases, the metal phosphate film can be provided in institute
The side surface for stating metal foil, can also be provided in the whole surface of metal foil.When the secondary cell is half-cell
It waits, the metal phosphate film can be provided only on the surface close to diaphragm side in metal foil；When the secondary cell is complete
Battery or for commercial battery group when, the metal phosphate film can be arranged in the both sides of metal foil being oppositely arranged
Surface.It is understood that can be reserved with the exposed region for soldering polar ear in metal foil, which is that metal will not be arranged
Phosphate layer.
In an embodiment of the present invention, the metal foil raw material and the solution containing phosphate radical are chemically reacted
Operation includes：
The metal foil raw material are immersed in the solution containing phosphate radical, impregnate 1 at a temperature of 0 DEG C -80 DEG C
- 600 minutes minutes；After immersion, secondary battery negative pole is made in washing, drying.
In the present invention embodiment, the metal foil raw material can be fully immersed in the solution containing phosphate radical
In, the metal foil that whole surface is both provided with fine and close metal phosphate film is obtained after reaction, then by metal foil far from diaphragm
Side surface on metal phosphate film polish off, obtain that the negative of metal phosphate film only is arranged in one side surface of metal foil
Pole；Or before immersion, protection materials are sticked into avoid the metal foil of this side and institute in the side of the metal foil raw material
The solution reaction containing phosphate radical is stated, then the metal foil raw material are immersed in the solution containing phosphate radical, in this way
After immersion, only metal phosphate film can be obtained in a side surface of metal foil raw material.
In the present invention embodiment, metal foil raw material are placed in the solution containing phosphate radical and carry out chemistry instead
It answers, to remove the oxide layer on metal foil raw material surface, reaction generates fine and close metal phosphate film, to improve battery
Efficiency for charge-discharge and cycle performance；Metal foil raw material are when with solution reaction containing phosphate radical, the solution containing phosphate radical
Corrosion can be carried out to metal foil raw material surface forms three-dimensional porous structure, the advantageous lithium ion of this structure is embedded and deviates from, to
Improve the high rate performance of battery.While corrosion, the metal phosphate in-situ deposition of phosphate radical and the formation of metal foil raw material
On the surface of metal foil raw material, the secondary battery negative pole is finally obtained, the secondary battery negative pole includes metal foil and sets
Set the fine and close metal phosphate film in the metal foil surface.Since corrosion reaction has occurred, the thickness of metal foil may be small
In the thickness of metal foil raw material.
In embodiment of the present invention, the solution containing phosphate radical includes phosphoric acid solution, phosphate dihydrogen salt solution, phosphoric acid
At least one of monohydric salt solution, pyrophosphate solution, pyrophosphate solution, metaphosphoric acid solution and metaphosphate solution；Specifically
Ground, the solution containing phosphate radical include phosphoric acid, sodium dihydrogen phosphate, disodium-hydrogen, pyrophosphoric acid, metaphosphoric acid, sodium pyrophosphate,
Potassium pyrophosphate, potassium dihydrogen phosphate, potassium phosphate,monobasic, sodium metaphosphate, potassium metaphosphate, cupric pyrophosphate, potassium phosphate, four metaphosphoric acids and six
At least one of sodium metaphosphate.Optionally, the mass fraction of the solute in the solution containing phosphate radical is 5%-85%；
Optionally, the solution containing phosphate radical is the oxyacid of phosphorus or the solution that its salt is mixed to form with water.
In embodiment of the present invention, the soaking time is -400 minutes 30 minutes, and soaking temperature is 10 DEG C -40 DEG C.
In embodiment of the present invention, the operation of the washing is metal foil raw material washing two after reacting to three times.
In embodiment of the present invention, the operation of the drying includes：Under the conditions of 40 DEG C -120 DEG C, drying 30 minutes -600 points
Clock.Optionally, the operation of the drying includes：Under the conditions of 80 DEG C -110 DEG C, dry -400 minutes 120 minutes.
In another embodiment of the present invention, fine and close gold is formed by way of deposition on metal foil raw material surface
Belong to phosphate layer operation include：
On metal foil raw material surface, deposited metal phosphate is formed by way of chemical vapor deposition or physical deposition
Secondary battery negative pole is made in fine and close metal phosphate film；The secondary battery negative pole includes metal foil and is arranged in the gold
Belong to the fine and close metal phosphate film on foil surface.
In embodiment of the present invention, in deposition process, a side surface of specific jig masking metal foil can be first used,
Ensure that the side surface is deposited without film；After deposition, the side surface setting metal phosphate only in metal foil can be obtained
Film.Metal foil raw material both side surface or all surface can also be both exposed in vapor deposition chamber, in metal foil
Both side surface or all surface be both provided with metal phosphate film.
Second aspect of the present invention provide preparation method it is simple to operation, cost is relatively low, can industrialized production, and be easy system
Obtain the secondary battery negative pole that homogeneity of product is high, structure is uniform, performance is stablized.
Third aspect present invention provides a kind of secondary cell, including anode, electrolyte, diaphragm and as described in relation to the first aspect
Cathode.
In embodiment of the present invention, when in cathode metal foil only a side surface is provided with metal phosphate film when, assembling electricity
When pond, the side of the metal foil for being provided with metal phosphate film and diaphragm are neighbouring, and are not provided with metal phosphate
The other side of film is far from diaphragm.
In embodiment of the present invention, the secondary cell that embodiment of the present invention provides can be lithium rechargeable battery, potassium
Ion secondary battery, magnesium ion secondary cell, sodium ion secondary battery, calcium ion secondary cell or Dual-ion cell, correspondingly,
The positive electrode active materials can be selected from the positive electrode active materials of conventional sodium ion secondary battery, lithium rechargeable battery just
Pole active material, the positive electrode active materials of magnesium ion secondary cell, the positive electrode active materials of sodium ion secondary battery, calcium ion two
The positive electrode active materials of primary cell or the positive electrode active materials of Dual-ion cell.Optionally, the anode of sodium ion secondary battery is living
Property material can be selected from phosphoric acid salt polyanionic compound containing sodium, tunnel structure compound, spinel oxides, stratiform
The one or more of transition metal oxide；Optionally, the positive electrode active materials of lithium rechargeable battery can be selected from lithium cobalt oxidation
Object, lithium nickel oxide, lithium manganese oxide or one or more of the polyanion positive electrode containing lithium；Specific such as ferric phosphate
Lithium, cobalt acid lithium, nickel-cobalt-manganternary ternary anode material；Optionally, the positive electrode active materials of magnesium ion secondary cell include the metal of magnesium
The one or more of oxide, metal sulfide or the polyanionic compound containing magnesium.Anode in the Dual-ion cell is living
Property material can be selected from it is one or more in carbon material, sulfide, nitride, oxide and carbide, still optionally further, institute
It includes graphite-like carbon material, vitreous carbon, carbon carbon composite, carbon fiber, hard carbon, porous charcoal, carbon black, carbon nanometer to state carbon material
It is one or more in pipe, graphene.
The graphite-like carbon material includes natural graphite, expanded graphite, artificial graphite, carbonaceous mesophase spherules graphite, pyrolysis
It is one or more in graphite, highly oriented graphite, three-dimensional graphite sponge.
The sulfide be selected from molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, ferrous disulfide, ferrous sulfide,
It is one or more in nickel sulfide, zinc sulphide, cobalt sulfide, manganese sulfide；The nitride is selected from hexagonal boron nitride, carbon adulterates six sides
It is one or more in boron nitride；The oxide is selected from molybdenum trioxide, tungstic acid, vanadic anhydride, vanadium dioxide, dioxy
Change one or more in titanium, zinc oxide, copper oxide, nickel oxide, manganese oxide；The carbide is selected from titanium carbide, ramet, carbon
Change one or more in molybdenum, silicon carbide.
The material of the plus plate current-collecting body includes any one in aluminium, copper, iron, tin, zinc, nickel, titanium, manganese, or containing extremely
A kind of few alloy of above-mentioned metallic element, or the composite material containing at least one above-mentioned metallic element.
In embodiment of the present invention, the electrolyte includes electrolyte and solvent, the electrolyte include lithium salts, sodium salt,
Sylvite, magnesium salts and calcium salt it is one or more；In the electrolyte, a concentration of 0.1mol/L-10mol/L of the electrolyte；
Specifically, lithium salts can be selected from the one or more of lithium hexafluoro phosphate, LiBF4, lithium perchlorate etc., further be chosen as six
Lithium fluophosphate；Sodium salt can be selected from sodium chloride, sodium fluoride, sodium sulphate, sodium carbonate, sodium phosphate, sodium nitrate, difluoro oxalate Boratex,
Sodium pyrophosphate, neopelex, lauryl sodium sulfate, trisodium citrate, kodalk, Boratex, sodium molybdate, tungsten
Sour sodium, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, sodium metasilicate, sodium lignin sulfonate, sodium hexafluoro phosphate, sodium oxalate, aluminic acid
Sodium, sodium methanesulfonate, sodium acetate, sodium dichromate, hexafluoroarsenate sodium, sodium tetrafluoroborate, sodium perchlorate, trifluoromethanesulfonimide
Sodium (NaTFSI), LiCF3SO3、LiN(SO2CF3)2One or more of, further it is chosen as sodium hexafluoro phosphate；Sylvite is optional
From potassium chloride, potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, difluoro oxalate potassium borate, potassium pyrophosphate, dodecyl
Benzene sulfonic acid potassium, dodecyl sulphate potassium, citric acid tri potassium, potassium metaborate, potassium borate, potassium molybdate, potassium tungstate, potassium bromide, nitrous
Sour potassium, Potassiumiodate, potassium iodide, potassium silicate, potassium lignosulfonate, potassium oxalate, potassium aluminate, pyrovinic acid potassium, potassium acetate, dichromic acid
Potassium, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium hyperchlorate, trifluoromethanesulfonimide potassium (KTFSI), KCF3SO3、KN(SO2CF3)2
In it is one or more, be further chosen as Potassium Hexafluorophosphate；Magnesium salts can be selected from organic magnesium salts or inorganic magnesium salt, wherein organic
Magnesium salts can select Grignard Reagent RMgX, including but not limited to methylphenylamine magnesium bromide, pyrrole radicals magnesium bromide, ethylenediamine tetrem
Acid disodium magnesium (EDTA-Mg), N, N- bis- (trimethyl silicon substrate) amino magnesium chloride, Mg (SnPh3)2、Mg(BR2R'2)2、Mg(AZ3- nRn'R'n”)2One or more of type complex, wherein R is alkyl, and X is halogen, A Al, B, As, P, Sb, Ta or Fe, Z
It is aryl for Cl or Br, R', and n'+n "=n, wherein inorganic magnesium salt can be selected from Mg (ClO4)2、Mg(BF4)2、Mg(PF6)2、
MgCl2、MgBr2、MgF2、MgI2、Mg(NO3)2、MgSO4、Mg(SCN)2、MgCrO4、Mg(CF3SO3)2One or more of；Calcium
Salt can be selected from hexafluorophosphoric acid calcium, tetrafluoro boric acid calcium, calcium chloride, calcium carbonate, calcium sulfate, calcium nitrate, calcirm-fluoride, trifluoromethanesulfonic acid
It is one or more in calcium, Calcium perchlorate.
In embodiment of the present invention, the solvent in electrolyte is not particularly limited, as long as electrolyte can be made to be dissociated into
Metal ion and anion, and metal ion and anion can be with free migrations.Specifically, the solvent can be non-aqueous
Based solvent or water-based solvent, the non-water solvents can be organic solvent or ionic liquid, the organic solvent be selected from esters,
The one or more of sulfone class, ethers etc., optional organic solvent can be selected from propene carbonate (PC), ethylene carbonate (EC), carbon
Diethyl phthalate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), N, N-
Dimethylacetylamide (DMA), fluorinated ethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA),
Gamma-butyrolacton (GBL), tetrahydrofuran (THF), 2- methyltetrahydrofurans (2MeTHF), 1,3- dioxolanes (DOL), 4- first
Base -1,3- dioxolanes (4MeDOL), dimethoxymethane (DMM), 1,2- diformazans Ethylene Oxide (DMP), triethylene glycol dimethyl ether
(DG), dimethyl sulfone (MSM), dimethyl ether (DME), ethylene sulfite (ES), sulfurous acid propylene fat (PS), two formicester of sulfurous acid
(DMS), one or more in sulfurous acid diethyl fat (DES), crown ether (12-crown-4), further it is chosen as methyl ethyl carbonate；Institute
It states ionic liquid and can be selected from 1- ethyl-3-methylimidazoles-hexafluorophosphate, 1- ethyl-3-methylimidazoles-tetrafluoroborate, 1-
Ethyl-3-methylimidazole-bis trifluoromethyl sulfimide salt, 1- propyl -3- methylimidazoles-hexafluorophosphate, 1- propyl -3- first
Base imidazoles-tetrafluoroborate, 1- propyl -3- methylimidazoles-bis trifluoromethyl sulfimide salt, 1- butyl -1- methylimidazoles-six
Fluorophosphate, 1- butyl -1- methylimidazoles-tetrafluoroborate, 1- butyl -1- methylimidazoles-bis trifluoromethyl sulfimide salt,
N- butyl-N- methylpyrrolidin- bis trifluoromethyls sulfimide salt, 1- butyl -1- methylpyrrolidin- bis trifluoromethyls sulphonyl are sub-
Amine salt, N- Methyl-N-propyls pyrrolidines-bis trifluoromethyl sulfimide salt, N- first, propylpiperdine-bis trifluoromethyl sulphonyl are sub-
Amine salt, N- first, it is one or more in butyl piperidine-bis trifluoromethyl sulfimide salt.
In embodiment of the present invention because grown one layer of electronic isolation on metal foil surface, metal ion such as lithium from
The metal phosphate film layer of son conducting so that greatly reduce the decomposition of electrolyte so that electricity during battery charging and discharging
The first efficiency for charge-discharge in pond, security performance effectively improve, so being easy to occur in cathode in charge and discharge process to some
Although they cannot be used alone on conventional battery system for the solvent of reduction reaction, can be used alone in this hair
In bright battery system.Such as propene carbonate (PC) can not individually or large scale is applied to existing battery system, but it can
To be used alone in the battery system of the present invention.
In embodiment of the present invention, in order to promote the formation of negative terminal surface solid electrolyte film (SEI), to improve cathode
Structural stability, service life and performance, can further be added additive in the electrolyte, and the additive can select
From the one or more of esters, sulfone class, ethers, nitrile and olefines etc., such as fluorinated ethylene carbonate, vinylene carbonate, carbon
Sour vinylethylene, 1,3- propane sultones, 1,4- butyl sultones, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethyl sulfate,
Ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, glycol sulfite, carbonochloridic acid
Formicester, dimethyl sulfoxide (DMSO), methyl phenyl ethers anisole, acetamide, diazine, metadiazine, crown ether 12-crown-4, crown ether 18- crown-s 6,4-
Fluoroanisole, fluoro chain ether, difluoromethyl ethylene carbonate, trifluoromethy ethylene carbonate, chlorocarbonic acid vinyl acetate,
Bromo ethylene carbonate, trifluoroethyl phosphonic acids, bromo butyrolactone, fluoroacetic base ethane, phosphate, phosphite ester, phosphonitrile, second
Hydramine, carbonization dimethylamine, cyclobutyl sulfone, 1,3- dioxolanes, acetonitrile, long-chain olefin, alundum (Al2O3), magnesia, oxidation
It is one or more in barium, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide, lithium carbonate, further it is chosen as carbonic acid Asia second
Enester (VC), mass fraction of the additive in the electrolyte are 0.1%-20%, and further alternative is 1%-
6%.
In embodiment of the present invention, the diaphragm material is not particularly limited, using the more of insulation commonly used in the art
Pore polymer film or inorganic porous film etc., as porous polypropylene film, porous polyethylene film, porous compound polymer are thin
Film, non-conductive fibre paper or porous ceramics diaphragm etc., use non-conductive fibre diaphragm still optionally further, such as fibreglass diaphragm
Deng.
The secondary cell that third aspect present invention provides, efficiency for charge-discharge, cycle performance, high rate performance, the height of battery
Warm nature energy and security performance are preferable.
In embodiment of the present invention, the preparation method of the secondary cell can be used that well known to a person skilled in the art various
Method, such as may comprise steps of：
(1) positive plate is prepared：Anode sizing agent is coated on plus plate current-collecting body and prepares anode；
(2) cathode is prepared：Using the secondary battery negative pole described in above-mentioned first aspect as cathode；
(3) it encapsulates：By anode, diaphragm and cathode stacks gradually or winding prepares Battery Pole Core, and post package is at battery.
Encapsulation in embodiment of the present invention includes that Battery Pole Core is put into battery case, welded cover plate and battery case
Body injects electrolyte, battery is melted into and is sealed, the technologies such as is melted into, seal using art technology in the cell housing
Various technologies, the present invention well known to personnel are not particularly limited.
The present invention is further described below in conjunction with specific embodiment, it should be understood that specific reality described herein
It applies example to be only used to explain the present invention, be not intended to limit the present invention.Raw material passes through quotient employed in embodiment and comparative example
It buys.
Lithium battery system implementation example 1-38：
A kind of preparation method of secondary battery negative pole, including：
The aluminium foil of 50 micron thickness, which is immersed in mass fraction, is 60 minutes in 50% phosphoric acid solution, then by the aluminium after reaction
Foil is cleaned to place to lead to three times afterwards with pure water carries out constant temperature drying in 300 minutes at a temperature of 80 DEG C in baking oven, you can obtain secondary electricity
Pond cathode.Finally required the cathode pole piece of treated secondary battery negative pole cuts into needs according to battery design.
Fig. 1 is scanning electron microscope (SEM) figure of normal aluminium foil；Fig. 2 is secondary cell made from the embodiment of the present invention 1
The SEM of cathode schemes；Fig. 3 is the enlarged drawing of the SEM figures of secondary battery negative pole made from the embodiment of the present invention 1；As shown in Figure 1, Figure 2, Fig. 3
Shown, aluminium foil surface after treatment is in three-dimensional porous structure, and this structure is conducive to reduce aluminium in battery charge and discharge process
Foil pole piece volume expansion, the advantageous cycle performance for improving battery.And the advantageous lithium ion of this porous structure is embedded and abjection, from
And improve the high rate performance of battery.The high performance battery of high power capacity can be prepared using the cathode.
Fig. 4 is X-ray energy spectrum (EDS) figure of secondary battery cathode pole surface made from the embodiment of the present invention 1.In order to characterize phosphorus
Acid treated aluminium foil whether there is phosphoric acid aluminum membranous layer, we carry out X-ray energy spectrum (EDS) to aluminium foil surface and analyze, analysis knot
Fruit shows aluminium foil surface with the presence of phosphorus, oxygen element, this illustrates that aluminium foil surface is that there are one layer thin of phosphoric acid aluminum membranous layers.Specifically
Test result is shown in Fig. 4：First Zhang Tu represents the distribution map of aluminium element, and the second Zhang Tu represents the distribution map of oxygen element, third generation
The distribution map of table P elements, the scale in figure are 10 μm.Figure 4, it is seen that secondary battery negative pole table produced by the present invention
Phosphorus and oxygen element are contained in face, illustrate that phosphoric acid aluminium film has been made on the surface of aluminium foil in the present invention.
Lithium battery system implementation example 1
The lithium iron phosphate positive material that specific capacity is 140mAh/g is pressed 95 with PVDF, conductive black:3:2 are coated in aluminium foil
It is upper to be used as positive plate.The processing technology of positive plate and process control are all made of the technology of current industrialization, finally will be above-mentioned
For secondary battery negative pole after processing in a normal way with above-mentioned anode, electrolyte is the ethylene carbonate of 1mol/LLiPF6
(EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio be=1：1), diaphragm is that celgard2400 polypropylene is porous
Film is assembled into full battery in the glove box full of argon gas and obtains battery sample C1.
Lithium battery system comparative example 1
Using the aluminium foil of 50 micron thickness as cathode.By specific capacity be 140mAh/g lithium iron phosphate positive material with
PVDF, conductive black press 95:3:2 are coated on aluminium foil as positive plate.The processing technology of positive plate and process control are all made of
The technology of industrialization at present, finally using the aluminium foil of positive plate and 50 micron thickness after processing as cathode pole piece, electrolysis
(volume ratio is=1 to the mixed solution for the ethylene carbonate (EC) and dimethyl carbonate (DMC) that liquid is 1mol/L LiPF6：1),
Diaphragm is assembled into full battery for celgard2400 polypropylene porous films in the glove box full of argon gas and obtains battery sample C0.
Other embodiment is adjusted relevant parameter and can be obtained different implementation with reference to the specific steps of embodiment 1
Case.Specific embodiment parameter and test structure see the table below 1.
1 embodiment supplemental characteristic of table and the performance test results
Remarks：When, containing there are two types of when compound, the volume ratio of two kinds of compounds is in the solution containing phosphate radical in table
1:1.As+30% phosphoric acid of 50% cupric pyrophosphate indicates that mass fraction divides for 50% copper pyrophosphate solution and quality in embodiment 12
The phosphoric acid solution that number is 30% is 1 according to volume ratio:1 is mixed to form the solution containing phosphate radical.
According to table 1 it is found that can effectively improve filling for battery by growing one layer of aluminum phosphate compound in aluminium foil surface
Discharging efficiency and cycle performance.
Aluminium-graphite Dual-ion cell system implementation example 1-38：
A kind of preparation method of secondary battery negative pole, including：
The aluminium foil of 50 micron thickness, which is immersed in mass fraction, is 60 minutes in 50% phosphoric acid solution, then by the aluminium after reaction
Foil is cleaned to place to lead to three times afterwards with pure water carries out constant temperature drying in 300 minutes at a temperature of 80 DEG C in baking oven, you can obtain secondary electricity
Pond cathode.Finally required the cathode pole piece of treated secondary battery negative pole cuts into needs according to battery design.
Aluminium-graphite Dual-ion cell system implementation example 1
The graphite positive electrode that specific capacity is 100mAh/g is pressed 95 with PVDF, conductive black:3:2 be coated in aluminium foil on make
For positive plate.The processing technology of positive plate and process control are all made of the technology of current industrialization, finally by above-mentioned processing
For secondary battery negative pole afterwards in a normal way with above-mentioned anode, electrolyte is the ethylene carbonate (EC) of 4mol/L LiPF6
(volume ratio is=1 with the mixed solution of methyl ethyl carbonate (EMC)：1)+2% sub- vinyl carbonate (VC), diaphragm are
Celgard2400 polypropylene porous films are assembled into full battery in the glove box full of argon gas and obtain battery sample C10.
Comparative example 1
Using the aluminium foil of 50 micron thickness as cathode.By graphite positive electrode and PVDF that specific capacity is 100mAh/g, lead
Electric carbon black presses 95:3:2 are coated in as positive plate on aluminium foil, and the processing technology of positive plate and process control are all made of current industry
The technology of change, it is 4mol/L LiPF6's finally to regard positive plate and the aluminium foil after processing as the pole piece of cathode, electrolyte
(volume ratio is=1 to the mixed solution of ethylene carbonate (EC) and methyl ethyl carbonate (EMC)：1)+2% sub- vinyl carbonate (VC),
Diaphragm is assembled into full battery for celgard2400 polypropylene porous films in the glove box full of argon gas and obtains battery sample C00.
The specific steps of Dual-ion cell other embodiment reference aluminium-graphite Dual-ion cell system implementation example 1, to correlation
Parameter, which is adjusted, can be obtained different case study on implementation.Specific embodiment parameter and test structure see the table below 2.
2 embodiment supplemental characteristic of table and the performance test results
Remarks：When, containing there are two types of when compound, the volume ratio of two kinds of compounds is in the solution containing phosphate radical in table
1:1.As+30% phosphoric acid of 50% cupric pyrophosphate indicates that mass fraction divides for 50% copper pyrophosphate solution and quality in embodiment 12
The phosphoric acid solution that number is 30% is 1 according to volume ratio:1 is mixed to form the solution containing phosphate radical.
According to table 2 it is found that can effectively improve filling for battery by growing one layer of aluminum phosphate compound in aluminium foil surface
Discharging efficiency and cycle performance.
The foil of unlike material-graphite Dual-ion cell system implementation example 1-16
The foil of unlike material and graphite are assembled into battery and carry out forming test by the embodiment of the present invention, wherein for every
A kind of foil has all carried out not carrying out the comparison of phosphoric acid processing and progress phosphoric acid processing, and specific prepare can refer to reality with test method
The specific steps for applying example 1 are adjusted relevant parameter and can be obtained different case study on implementation.Specific assembling test result such as table
Shown in 3.
3 embodiment supplemental characteristic of table and the performance test results
From table 3 it can be seen that electric after the cathode assembled battery that the metal foil of unlike material obtains after peroxophosphoric acid is handled
The first charge discharge efficiency and cycle performance in pond are effectively improved.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (11)
1. a kind of secondary battery negative pole, which is characterized in that including metal foil and the fine and close gold in the metal foil surface is arranged
Belong to phosphate layer, the metal foil is used as negative current collector and negative electrode active material simultaneously, the material of the metal foil include aluminium,
Any one in copper, iron, tin, zinc, nickel, manganese, lead, antimony, cadmium and bismuth, or the alloy containing at least one above-mentioned metallic element；
The material of the metal phosphate film includes aluminum phosphate, cupric phosphate, ferric phosphate, phosphoric acid tin, trbasic zinc phosphate, nickel phosphate, manganese phosphate, phosphorus
It is one or more in lead plumbate, phosphoric acid antimony, cadmium phosphate and bismuth phosphate.
2. secondary battery negative pole as described in claim 1, which is characterized in that the source metal in the metal phosphate film and institute
The metallic element stated in metal foil is identical.
3. secondary battery negative pole as described in claim 1, which is characterized in that the surface layer of the metal foil has three-dimensional porous knot
Structure, porous pore size are 10nm-20 μm.
4. secondary battery negative pole as claimed in claim 3, which is characterized in that the thickness on the surface layer is 1nm-10 μm, described
The thickness on surface layer and the thickness ratio of the metal foil are 1:10-10000.
5. secondary battery negative pole as described in claim 1, which is characterized in that the thickness of the metal phosphate film is 1nm-3 μ
The thickness ratio of m, the metal phosphate film thickness and the metal foil is 1:30-10000.
6. a kind of preparation method of secondary battery negative pole, which is characterized in that including：
Metal foil raw material are provided, the metal foil raw material and the solution containing phosphate radical are subjected to chemical reaction or in institute
It states metal foil raw material surface and forms fine and close metal phosphate film by way of deposition, secondary battery negative pole is made；
The secondary battery negative pole includes metal foil and the fine and close metal phosphate film in the metal foil surface is arranged, described
Metal foil is used as negative current collector and negative electrode active material simultaneously, the material of the metal foil include aluminium, copper, iron, tin, zinc, nickel,
Any one in manganese, lead, antimony, cadmium and bismuth, or the alloy containing at least one above-mentioned metallic element；The metal phosphate film
Material include aluminum phosphate, cupric phosphate, ferric phosphate, phosphoric acid tin, trbasic zinc phosphate, nickel phosphate, manganese phosphate, lead phosphate, phosphoric acid antimony, phosphoric acid
It is one or more in cadmium and bismuth phosphate.
7. the preparation method of secondary battery negative pole as claimed in claim 6, which is characterized in that by the metal foil raw material with
The operation that solution containing phosphate radical is chemically reacted includes：
The metal foil raw material are immersed in the solution containing phosphate radical, impregnated at a temperature of 0 DEG C -80 DEG C 1 minute -
600 minutes；After immersion, secondary battery negative pole is made in washing, drying.
8. the preparation method of secondary battery negative pole as claimed in claim 7, which is characterized in that the solution containing phosphate radical
Including phosphoric acid solution, phosphate dihydrogen salt solution, dibasic alkaliine solution, pyrophosphate solution, pyrophosphate solution, metaphosphoric acid solution
At least one of with metaphosphate solution；The mass fraction of solute in the solution containing phosphate radical is 5%-85%.
9. the preparation method of secondary battery negative pole as claimed in claim 7, which is characterized in that the operation of the drying includes：
Under the conditions of 40 DEG C -120 DEG C, dry -600 minutes 30 minutes.
10. a kind of secondary cell, which is characterized in that including anode, electrolyte, diaphragm and as described in claim any one of 1-5
Cathode.
11. secondary cell as claimed in claim 10, which is characterized in that the electrolyte includes electrolyte and solvent, described
Electrolyte includes the one or more of lithium salts, sodium salt, sylvite, magnesium salts and calcium salt；In the electrolyte, the concentration of the electrolyte
For 0.1mol/L-10mol/L.
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| CN112670510A (en) * | 2020-12-23 | 2021-04-16 | 中南大学 | NaCrO2@ MFx/C composite material, preparation method thereof and application thereof in sodium-ion battery |
| CN113753876A (en) * | 2021-07-20 | 2021-12-07 | 中南大学 | Potassium ion battery negative electrode material and preparation method thereof |
| CN114927668A (en) * | 2022-06-13 | 2022-08-19 | 海城申合科技有限公司 | Preparation method of nitrogen-doped antimony phosphate/carbon composite material for negative electrode of sodium ion battery |
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| CN114927668A (en) * | 2022-06-13 | 2022-08-19 | 海城申合科技有限公司 | Preparation method of nitrogen-doped antimony phosphate/carbon composite material for negative electrode of sodium ion battery |
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