CN107039639A - A kind of preparation method of high power capacity sodium-ion battery - Google Patents

A kind of preparation method of high power capacity sodium-ion battery Download PDF

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Publication number
CN107039639A
CN107039639A CN201710095504.XA CN201710095504A CN107039639A CN 107039639 A CN107039639 A CN 107039639A CN 201710095504 A CN201710095504 A CN 201710095504A CN 107039639 A CN107039639 A CN 107039639A
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sodium
ion battery
preparation
solution
high power
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李风浪
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Dongguan Lianzhou Intellectual Property Operation and Management Co Ltd
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Dongguan Lianzhou Intellectual Property Operation and Management Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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

Abstract

The invention discloses a kind of preparation method of high power capacity sodium-ion battery, comprise the following steps：Sodium ion positive electrode is made using sodium oxalate, ferrous oxalate sodium ferrocyanide as raw material first；Then mesoporous TiO 2 graphene composite material is prepared as negative material using hydro-thermal method；Positive electrode and negative material are mixed to prepare slurry, coating and collection liquid surface with binding agent, conductive agent respectively, positive plate and negative plate is made in tabletting；Finally by positive plate obtained above, the overlapping placement of negative plate, centre is separated with barrier film, with nickel wire extraction electrode, and electrolyte solution wetting electrode is added dropwise, and Vacuum Package obtains sodium-ion battery.The capacity of sodium-ion battery produced by the present invention is up to 202.5mAh/g, and 1000 capacity are circulated under 10.5C multiplying power and are not lost substantially, and asepsis environment-protecting, and cost is low.

Description

A kind of preparation method of high power capacity sodium-ion battery
Technical field：
The present invention relates to field of cell preparation, a kind of preparation method of high power capacity sodium-ion battery is specifically related to.
Background technology：
Energy storage technology is all kinds of energy application demands of balance, lifts the effective means of social integral energy service efficiency, Improving the application fields such as extensive and distribution type renewable energy access capability, the lifting of city micro net power quality has widely Prospect of the application, while being also one of critical support technology that intelligent grid is built.In all kinds of energy storage technologies, electrochemical energy storage skill Art is an important branch.The carrier of electrochemical energy storage is battery, and in existing energy-storage battery system, lithium ion battery is with its material Material system is flexible, technology innovation fast, as energy-storage battery system of greatest concern, the extensive use in all kinds of demonstration projects. But, current lithium ion battery safety problem is not yet solved at all, and battery cost is higher, and with scale energy storage and electronic The popularization and application of automotive engineering, lithium ion battery is in the following bottleneck for being likely to be encountered lithium resource dependence.
As the metallic element of the same clan with elemental lithium, every physicochemical properties of sodium and lithium are closer to, and in nature Boundary contains abundant (elements of earth's crust reserves the 4th), and reserves are far above the lithium resource for focusing primarily upon South America, while extracting relative It is easier.The research and development of sodium-ion battery can relax the battery development triggered by lithium resource shortage and be limited to a certain extent Problem.If developing the material of function admirable, safety and stability on this basis, sodium-ion battery will possess bigger than lithium battery Market competition advantage.According to current progress, sodium-ion battery has 3 outstanding advantages compared with lithium ion battery：1. it is former Expect aboundresources, it is with low cost, it is widely distributed；2. the half-cell potential of sodium-ion battery 0.3~0.4V high compared with lithium ion potential, Can be using decomposition potential lower electrolyte solvent and electrolytic salt, the range of choice of electrolyte is wider；3. sode cell has phase To stable chemical property, use is safer.At the same time, there is also defect, the phase of such as sodium element for sodium-ion battery It is much higher to atom mass rate lithium, cause theoretical specific capacity small, the 1/2 of not enough lithium；Sodium ion radius ratio lithium ion radius is big 70% so that sodium ion insertion in battery material is more difficult to abjection.
The content of the invention：
It is an object of the invention to provide a kind of preparation method of high power capacity sodium-ion battery, this method is simple to operate, is made Sodium-ion battery capacity it is big, good cycling stability, service life is long.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of high power capacity sodium-ion battery, comprises the following steps：
(1) preparation of positive plate：
1) sodium oxalate, ferrous oxalate and deionized water are mixed evenly, obtained solution A；Sodium ferrocyanide and it will go Ionized water is mixed evenly, obtained solution B；
2) surfactant is added into solution B, ultrasonic agitation obtains solution C, and by solution A ultrasonic agitation, ultrasound is finished After add solution C, and stir 30-100h at 20-30 DEG C, obtain blue precipitate；By blue precipitate obtained above spend from Sub- water washing 4-5 times, is then washed 2-3 times with methanol, is dried in vacuo 12-24h, is obtained sodium ion positive electrode；
3) sodium ion positive electrode obtained above, conductive agent, binding agent are mixed into slurry and are applied to afflux body surface Face, sodium-ion battery positive plate is made in vacuum drying, tabletting；
(2) preparation of negative plate
Using mesoporous TiO 2-graphene composite material as negative material, then by negative material and conductive agent, viscous Knot agent stirring is mixed into slurry, is coated on collection liquid surface, and sodium-ion battery negative plate is made in tabletting；
(3) battery is assembled
By positive plate obtained above, the overlapping placement of negative plate, centre is separated with barrier film, with nickel wire extraction electrode, is added dropwise Electrolyte solution wetting electrode, Vacuum Package obtains sodium-ion battery.
It is used as the preferred of above-mentioned technical proposal, step 1) in, solution A mesoxalic acid is ferrous, the molar concentration of sodium oxalate is (0.1-1)mol/L、(0.01-0.9)mol/L。
It is used as the preferred of above-mentioned technical proposal, step 1) in, the molar concentration of sodium ferrocyanide is 0.88- in solution B 1.5mol/L。
It is used as the preferred of above-mentioned technical proposal, step 2) in, the surfactant is F127.
It is used as the preferred of above-mentioned technical proposal, step 3) in, vacuum drying temperature is 100-125 DEG C.
It is used as the preferred of above-mentioned technical proposal, step 2) in, before ultrasonic agitation processing solution A, solution A need to be stirred To clarification.
As the preferred of above-mentioned technical proposal, in step (2), the preparation method tool of the mesoporous TiO 2-graphene Body is：Isopropyl titanate is dissolved in organic fatty alcohol, organic aliphatic acid is added and is mixed evenly, and adds graphene, It is transferred to after well mixed at water heating kettle, 110-130 DEG C and reacts 10-20h, after reaction terminates, be cooled to room temperature, is centrifuged, precipitation It is washed with deionized, is dried in vacuo 5-10h, obtains mesoporous TiO 2-graphene composite material.
As the preferred of above-mentioned technical proposal, isopropyl titanate, the mass ratio of graphene are (1-1.6)：1.
As the preferred of above-mentioned technical proposal, isopropyl titanate, organic aliphatic acid, the volume ratio of organic fatty alcohol are 1:5： (45-50)。
As the preferred of above-mentioned technical proposal, in step (3), the solvent of the electrolyte solution is ethylene carbonate, carbon One kind in acid propylene ester, diethyl carbonate, l, 2- dimethoxy-ethanes, tetrahydrofuran, the solute of electrolyte solution is NaPF6、NaClO4、NaAlCl4、NaFeCl4、NaSO3CF3In one kind.
Compared with prior art, the present invention has advantages below：
(1) sodium ion positive pole material is made as raw material using sodium oxalate, ferrous oxalate, sodium ferrocyanide by the present invention first Material, the low in raw material price effectively reduces the preparation cost of battery, and the bit constant of matching somebody with somebody of oxalate and ferrous ion is less than Asia Iron atom in cyanogen root and ferrous ion, ferrous oxalate can slowly discharge and is coordinated with ferrous cyanogen root, so as to control material The speed of growth so that obtained sodium ion positive electrode defect is low, and capacity is big；
(2) on the other hand, the present invention is using mesoporous TiO 2-graphene as negative material, and titanium dioxide is steady Qualitative good, it is easy to synthesize, nontoxic, its meso-hole structure can reduce sodium ion migration distance, can also improve motor and electrolyte Contact area, so as to ensure more preferable electrochemical reaction, mesoporous TiO 2-graphene composite material specific surface area is big, conductive Property is good, and chemical stability is good.
Embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solution The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of preparation method of high power capacity sodium-ion battery, comprises the following steps：
(1) preparation of positive plate：
1) sodium oxalate, ferrous oxalate and deionized water are mixed evenly, obtained solution A；Sodium ferrocyanide and it will go Ionized water is mixed evenly, obtained solution B；Wherein, solution A mesoxalic acid is ferrous, sodium oxalate molar concentration is 0.1mol/L, The molar concentration of sodium ferrocyanide is 0.88mol/L in 0.01mol/L, solution B；
2) F127 is added into solution B, ultrasonic agitation obtains solution C, solution A is stirred to clarify, and then ultrasound is stirred Mix, ultrasound adds solution C after finishing, and stirs 30h at 20-30 DEG C, obtains blue precipitate；By blue precipitate obtained above It is washed with deionized 4-5 times, is then washed 2-3 times with methanol, 12h is dried in vacuo at 100 DEG C, obtains sodium ion positive pole material Material；
3) sodium ion positive electrode obtained above, conductive agent, binding agent are mixed into slurry and are applied to afflux body surface Face, sodium-ion battery positive plate is made in vacuum drying, tabletting；
(2) preparation of negative plate
Isopropyl titanate is dissolved in organic fatty alcohol, organic aliphatic acid is added and is mixed evenly, and add graphite Alkene, is transferred at water heating kettle, 110 DEG C after being well mixed and reacts 10h, after reaction terminates, is cooled to room temperature, centrifuges, and precipitation is spent Ion water washing, is dried in vacuo 5h, obtains mesoporous TiO 2-graphene；Wherein, the mass ratio of isopropyl titanate, graphene For 1：1, isopropyl titanate, organic aliphatic acid, the volume ratio of organic fatty alcohol are 1:5：45；
Using obtained mesoporous TiO 2-graphene composite material as negative material, then by negative material with leading Electric agent, binding agent stirring are mixed into slurry, are coated on collection liquid surface, and sodium-ion battery negative plate is made in tabletting；
(3) battery is assembled
By positive plate obtained above, the overlapping placement of negative plate, centre is separated with barrier film, with nickel wire extraction electrode, is added dropwise Electrolyte solution wetting electrode, Vacuum Package obtains sodium-ion battery；
Wherein, the solvent of electrolyte solution is tetrahydrofuran, and the solute of electrolyte solution is NaSO3CF3。
Embodiment 2
A kind of preparation method of high power capacity sodium-ion battery, comprises the following steps：
(1) preparation of positive plate：
1) sodium oxalate, ferrous oxalate and deionized water are mixed evenly, obtained solution A；Sodium ferrocyanide and it will go Ionized water is mixed evenly, obtained solution B；Wherein, solution A mesoxalic acid is ferrous, sodium oxalate molar concentration is 0.3mol/L, The molar concentration of sodium ferrocyanide is 0.95mol/L in 0.2mol/L, solution B；
2) F127 is added into solution B, ultrasonic agitation obtains solution C, solution A is stirred to clarify, and then ultrasound is stirred Mix, ultrasound adds solution C after finishing, and stirs 40h at 20-30 DEG C, obtains blue precipitate；By blue precipitate obtained above It is washed with deionized 4-5 times, is then washed 2-3 times with methanol, 14h is dried in vacuo at 100 DEG C, obtains sodium ion positive pole material Material；
3) sodium ion positive electrode obtained above, conductive agent, binding agent are mixed into slurry and are applied to afflux body surface Face, sodium-ion battery positive plate is made in vacuum drying, tabletting；
(2) preparation of negative plate
Isopropyl titanate is dissolved in organic fatty alcohol, organic aliphatic acid is added and is mixed evenly, and add graphite Alkene, is transferred at water heating kettle, 110 DEG C after being well mixed and reacts 12h, after reaction terminates, is cooled to room temperature, centrifuges, and precipitation is spent Ion water washing, is dried in vacuo 6h, obtains mesoporous TiO 2-graphene；Wherein, the mass ratio of isopropyl titanate, graphene For 1.1：1, isopropyl titanate, organic aliphatic acid, the volume ratio of organic fatty alcohol are 1:5：46；
Using obtained mesoporous TiO 2-graphene composite material as negative material, then by negative material with leading Electric agent, binding agent stirring are mixed into slurry, are coated on collection liquid surface, and sodium-ion battery negative plate is made in tabletting；
(3) battery is assembled
By positive plate obtained above, the overlapping placement of negative plate, centre is separated with barrier film, with nickel wire extraction electrode, is added dropwise Electrolyte solution wetting electrode, Vacuum Package obtains sodium-ion battery；
Wherein, the solvent of electrolyte solution is propene carbonate, and the solute of electrolyte solution is NaClO4。
Embodiment 3
A kind of preparation method of high power capacity sodium-ion battery, comprises the following steps：
(1) preparation of positive plate：
1) sodium oxalate, ferrous oxalate and deionized water are mixed evenly, obtained solution A；Sodium ferrocyanide and it will go Ionized water is mixed evenly, obtained solution B；Wherein, solution A mesoxalic acid is ferrous, sodium oxalate molar concentration is 0.4mol/L, The molar concentration of sodium ferrocyanide is 1.05mol/L in 0.3mol/L, solution B；
2) F127 is added into solution B, ultrasonic agitation obtains solution C, solution A is stirred to clarify, and then ultrasound is stirred Mix, ultrasound adds solution C after finishing, and stirs 50h at 20-30 DEG C, obtains blue precipitate；By blue precipitate obtained above It is washed with deionized 4-5 times, is then washed 2-3 times with methanol, 16h is dried in vacuo at 105 DEG C, obtains sodium ion positive pole material Material；
3) sodium ion positive electrode obtained above, conductive agent, binding agent are mixed into slurry and are applied to afflux body surface Face, sodium-ion battery positive plate is made in vacuum drying, tabletting；
(2) preparation of negative plate
Isopropyl titanate is dissolved in organic fatty alcohol, organic aliphatic acid is added and is mixed evenly, and add graphite Alkene, is transferred at water heating kettle, 110 DEG C after being well mixed and reacts 14h, after reaction terminates, is cooled to room temperature, centrifuges, and precipitation is spent Ion water washing, is dried in vacuo 7h, obtains mesoporous TiO 2-graphene；Wherein, the mass ratio of isopropyl titanate, graphene For 1.2：1, isopropyl titanate, organic aliphatic acid, the volume ratio of organic fatty alcohol are 1:5：47；
Using obtained mesoporous TiO 2-graphene composite material as negative material, then by negative material with leading Electric agent, binding agent stirring are mixed into slurry, are coated on collection liquid surface, and sodium-ion battery negative plate is made in tabletting；
(3) battery is assembled
By positive plate obtained above, the overlapping placement of negative plate, centre is separated with barrier film, with nickel wire extraction electrode, is added dropwise Electrolyte solution wetting electrode, Vacuum Package obtains sodium-ion battery；
Wherein, the solvent of electrolyte solution is diethyl carbonate, and the solute of electrolyte solution is NaAlCl4。
Embodiment 4
A kind of preparation method of high power capacity sodium-ion battery, comprises the following steps：
(1) preparation of positive plate：
1) sodium oxalate, ferrous oxalate and deionized water are mixed evenly, obtained solution A；Sodium ferrocyanide and it will go Ionized water is mixed evenly, obtained solution B；Wherein, solution A mesoxalic acid is ferrous, sodium oxalate molar concentration is 0.6mol/L, The molar concentration of sodium ferrocyanide is 1.15mol/L in 0.5mol/L, solution B；
2) F127 is added into solution B, ultrasonic agitation obtains solution C, solution A is stirred to clarify, and then ultrasound is stirred Mix, ultrasound adds solution C after finishing, and stirs 60h at 20-30 DEG C, obtains blue precipitate；By blue precipitate obtained above It is washed with deionized 4-5 times, is then washed 2-3 times with methanol, 18h is dried in vacuo at 110 DEG C, obtains sodium ion positive pole material Material；
3) sodium ion positive electrode obtained above, conductive agent, binding agent are mixed into slurry and are applied to afflux body surface Face, sodium-ion battery positive plate is made in vacuum drying, tabletting；
(2) preparation of negative plate
Isopropyl titanate is dissolved in organic fatty alcohol, organic aliphatic acid is added and is mixed evenly, and add graphite Alkene, is transferred at water heating kettle, 115 DEG C after being well mixed and reacts 16h, after reaction terminates, is cooled to room temperature, centrifuges, and precipitation is spent Ion water washing, is dried in vacuo 7h, obtains mesoporous TiO 2-graphene；Wherein, the mass ratio of isopropyl titanate, graphene For 1.4：1, isopropyl titanate, organic aliphatic acid, the volume ratio of organic fatty alcohol are 1:5：47；
Using obtained mesoporous TiO 2-graphene composite material as negative material, then by negative material with leading Electric agent, binding agent stirring are mixed into slurry, are coated on collection liquid surface, and sodium-ion battery negative plate is made in tabletting；
(3) battery is assembled
By positive plate obtained above, the overlapping placement of negative plate, centre is separated with barrier film, with nickel wire extraction electrode, is added dropwise Electrolyte solution wetting electrode, Vacuum Package obtains sodium-ion battery；
Wherein, the solvent of electrolyte solution is l, and 2- dimethoxy-ethanes, the solute of electrolyte solution is NaAlCl4。
Embodiment 5
A kind of preparation method of high power capacity sodium-ion battery, comprises the following steps：
(1) preparation of positive plate：
1) sodium oxalate, ferrous oxalate and deionized water are mixed evenly, obtained solution A；Sodium ferrocyanide and it will go Ionized water is mixed evenly, obtained solution B；Wherein, solution A mesoxalic acid is ferrous, sodium oxalate molar concentration is 0.8mol/L, The molar concentration of sodium ferrocyanide is 1.45mol/L in 0.7mol/L, solution B；
2) F127 is added into solution B, ultrasonic agitation obtains solution C, solution A is stirred to clarify, and then ultrasound is stirred Mix, ultrasound adds solution C after finishing, and stirs 80h at 20-30 DEG C, obtains blue precipitate；By blue precipitate obtained above It is washed with deionized 4-5 times, is then washed 2-3 times with methanol, 20h is dried in vacuo at 120 DEG C, obtains sodium ion positive pole material Material；
3) sodium ion positive electrode obtained above, conductive agent, binding agent are mixed into slurry and are applied to afflux body surface Face, sodium-ion battery positive plate is made in vacuum drying, tabletting；
(2) preparation of negative plate
Isopropyl titanate is dissolved in organic fatty alcohol, organic aliphatic acid is added and is mixed evenly, and add graphite Alkene, is transferred at water heating kettle, 125 DEG C after being well mixed and reacts 18h, after reaction terminates, is cooled to room temperature, centrifuges, and precipitation is spent Ion water washing, is dried in vacuo 8h, obtains mesoporous TiO 2-graphene；Wherein, the mass ratio of isopropyl titanate, graphene For 1.4：1, isopropyl titanate, organic aliphatic acid, the volume ratio of organic fatty alcohol are 1:5：48；
Using obtained mesoporous TiO 2-graphene composite material as negative material, then by negative material with leading Electric agent, binding agent stirring are mixed into slurry, are coated on collection liquid surface, and sodium-ion battery negative plate is made in tabletting；
(3) battery is assembled
By positive plate obtained above, the overlapping placement of negative plate, centre is separated with barrier film, with nickel wire extraction electrode, is added dropwise Electrolyte solution wetting electrode, Vacuum Package obtains sodium-ion battery；
Wherein, the solvent of electrolyte solution is ethylene carbonate, and the solute of electrolyte solution is NaSO3CF3。
Embodiment 6
A kind of preparation method of high power capacity sodium-ion battery, comprises the following steps：
(1) preparation of positive plate：
1) sodium oxalate, ferrous oxalate and deionized water are mixed evenly, obtained solution A；Sodium ferrocyanide and it will go Ionized water is mixed evenly, obtained solution B；Wherein, solution A mesoxalic acid is ferrous, sodium oxalate molar concentration is 0.1mol/L, The molar concentration of sodium ferrocyanide is 1.5mol/L in 0.9mol/L, solution B；
2) F127 is added into solution B, ultrasonic agitation obtains solution C, solution A is stirred to clarify, and then ultrasound is stirred Mix, ultrasound adds solution C after finishing, and stirs 100h at 20-30 DEG C, obtains blue precipitate；Blueness obtained above is heavy Shallow lake is washed with deionized 4-5 times, is then washed 2-3 times with methanol, and 24h is dried in vacuo at 125 DEG C, obtains sodium ion positive pole material Material；
3) sodium ion positive electrode obtained above, conductive agent, binding agent are mixed into slurry and are applied to afflux body surface Face, sodium-ion battery positive plate is made in vacuum drying, tabletting；
(2) preparation of negative plate
Isopropyl titanate is dissolved in organic fatty alcohol, organic aliphatic acid is added and is mixed evenly, and add graphite Alkene, is transferred at water heating kettle, 130 DEG C after being well mixed and reacts 20h, after reaction terminates, is cooled to room temperature, centrifuges, and precipitation is spent Ion water washing, is dried in vacuo 10h, obtains mesoporous TiO 2-graphene；Wherein, the mass ratio of isopropyl titanate, graphene For 1.6：1, isopropyl titanate, organic aliphatic acid, the volume ratio of organic fatty alcohol are 1:5：50；
Using obtained mesoporous TiO 2-graphene composite material as negative material, then by negative material with leading Electric agent, binding agent stirring are mixed into slurry, are coated on collection liquid surface, and sodium-ion battery negative plate is made in tabletting；
(3) battery is assembled
By positive plate obtained above, the overlapping placement of negative plate, centre is separated with barrier film, with nickel wire extraction electrode, is added dropwise Electrolyte solution wetting electrode, Vacuum Package obtains sodium-ion battery；
Wherein, the solvent of electrolyte solution is that the solute of ethylene carbonate electrolyte solution is NaPF6。
Comparative example 1
Negative plate and the preparation method of assembling are same as Example 6, in the preparation of positive plate, solution A mesoxalic acid ferrous iron, The molar concentration of sodium oxalate is that the molar concentration of sodium ferrocyanide in 0.1mol/L, 1.5mol/L, solution B is 1.5mol/L.
Comparative example 2
Negative plate and the preparation method of assembling are same as Example 6, in the preparation of positive plate, solution A mesoxalic acid ferrous iron, The molar concentration of sodium oxalate is that the molar concentration of sodium ferrocyanide in 1.3mol/L, 0.9mol/L, solution B is 1.5mol/L.
Comparative example 3
Negative plate and the preparation method of assembling are same as Example 6, in the preparation of positive plate, solution A mesoxalic acid ferrous iron, The molar concentration of sodium oxalate is that the molar concentration of sodium ferrocyanide in 0.1mol/L, 1.5mol/L, solution B is 2mol/L.
Comparative example 4
The method and embodiment 6 of positive plate and assembling is identical, and negative material uses mesoporous TiO 2.
Comparative example 5
The method and embodiment 6 of positive plate and assembling is identical, and negative material uses titanium dioxide/graphene composite material.
Charge-discharge performance is tested：
The Land2001A types cell tester of Wuhan Lan electricity companies manufacture performs a series of cycle charge discharges to obtained battery Electrical testing, the first charge-discharge capacity of main test battery, cycle charge discharge electrical property.
Test operating procedure is：Battery after standing is accessed into Land2011A test systems by fixture, to assembling Good sodium-ion battery first carries out discharging and then charging, and the voltage range of discharge and recharge is 0.005V-3.0V or 0.005V- 2.5V, is often discharged and stands 5min after once terminating, recharge and 5min is stood after once terminating, and circulation is carried out.Test result is as follows It is shown：
First charge-discharge capacity under 10.5C multiplying powers, mA h/g Capacity under 10.5C multiplying powers under circulation 1000, mA h/g
Embodiment 1 199.9 199.9
Embodiment 2 192.0 192.0
Embodiment 3 198.5 198.3
Embodiment 4 202.5 202.0
Embodiment 5 190.7 190.3
Embodiment 6 198.8 197.8
Comparative example 1 173.5 173.5
Comparative example 2 163.5 109.5
Comparative example 3 160.5 100.9
Comparative example 4 168.8 132.1
Comparative example 5 139.5 108.7
From the point of view of above-mentioned data, sodium-ion battery capacity produced by the present invention is big, good cycling stability.Sodium-ion battery is just Pole material prepares mesoxalic acid sodium, ferrous oxalate, the consumption of sodium ferrocyanide also to have a great impact to the performance of battery, mainly Because the consumption of each component directly influences the speed of growth and size of positive electrode.Negative material uses mesoporous two During titanium oxide, relative to titanium dioxide more preferably, obtained battery capacity is also bigger for its electric conductivity, and stable charge/discharge is also got over It is good.

Claims (10)

1. a kind of preparation method of high power capacity sodium-ion battery, it is characterised in that comprise the following steps：
(1) preparation of positive plate：
1) sodium oxalate, ferrous oxalate and deionized water are mixed evenly, obtained solution A；By sodium ferrocyanide and deionization Water is mixed evenly, obtained solution B；
2) surfactant is added into solution B, ultrasonic agitation obtains solution C, by solution A ultrasonic agitation, ultrasound adds after finishing Enter solution C, and 30-100h is stirred at 20-30 DEG C, obtain blue precipitate；By blue precipitate deionized water obtained above Washing 4-5 times, is then washed 2-3 times with methanol, is dried in vacuo 12-24h, is obtained sodium ion positive electrode；
3) sodium ion positive electrode obtained above, conductive agent, binding agent are mixed into slurry and are applied to collection liquid surface, very Empty drying, tabletting, are made sodium-ion battery positive plate；
(2) preparation of negative plate
Using mesoporous TiO 2-graphene composite material as negative material, then by negative material and conductive agent, binding agent Stirring is mixed into slurry, is coated on collection liquid surface, and sodium-ion battery negative plate is made in tabletting；
(3) battery is assembled
By positive plate obtained above, the overlapping placement of negative plate, centre is separated with barrier film, with nickel wire extraction electrode, and electrolysis is added dropwise Matter solution-wet electrode, Vacuum Package obtains sodium-ion battery.
2. a kind of preparation method of high power capacity sodium-ion battery as claimed in claim 1, it is characterised in that：Step 1) in, it is molten Liquid A mesoxalic acids are ferrous, the molar concentration of sodium oxalate is (0.1-1) mol/L, (0.01-0.9) mol/L.
3. a kind of preparation method of high power capacity sodium-ion battery as claimed in claim 1, it is characterised in that：Step 1) in, it is molten The molar concentration of sodium ferrocyanide is 0.88-1.5mol/L in liquid B.
4. a kind of preparation method of high power capacity sodium-ion battery as claimed in claim 1, it is characterised in that：Step 2) in, institute Surfactant is stated for F127.
5. a kind of preparation method of high power capacity sodium-ion battery as claimed in claim 1, it is characterised in that：Step 3) in, very The temperature that sky is dried is 100-125 DEG C.
6. a kind of preparation method of high power capacity sodium-ion battery as claimed in claim 1, it is characterised in that：Step 2) in, Before ultrasonic agitation processing solution A, solution A need to be stirred to clarify.
7. a kind of preparation method of high power capacity sodium-ion battery as claimed in claim 1, it is characterised in that：In step (2), institute The preparation method for giving an account of porous titanium dioxide-graphene is specially：Isopropyl titanate is dissolved in organic fatty alcohol, added organic Aliphatic acid is mixed evenly, and adds graphene, is transferred to after being well mixed at water heating kettle, 110-130 DEG C and reacts 10-20h, After reaction terminates, be cooled to room temperature, centrifuge, precipitation is washed with deionized, be dried in vacuo 5-10h, obtain mesoporous TiO 2- Graphene composite material.
8. a kind of preparation method of high power capacity sodium-ion battery as claimed in claim 7, it is characterised in that：Isopropyl titanate, The mass ratio of graphene is (1-1.6)：1.
9. a kind of preparation method of high power capacity sodium-ion battery as claimed in claim 7, it is characterised in that：Isopropyl titanate, Organic aliphatic acid, the volume ratio of organic fatty alcohol are 1:5：(45-50).
10. a kind of preparation method of high power capacity sodium-ion battery as claimed in claim 1, it is characterised in that：In step (3), The solvent of the electrolyte solution is ethylene carbonate, propene carbonate, diethyl carbonate, l, 2- dimethoxy-ethanes, tetrahydrochysene One kind in furans, the solute of electrolyte solution is NaPF6、NaClO4、NaAlCl4、NaFeCl4、NaSO3CF3In one kind.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807923A (en) * 2018-06-21 2018-11-13 清远佳致新材料研究院有限公司 The preparation method of sodium-ion battery modifying titanium dioxide-graphene negative material
CN110400702A (en) * 2019-04-15 2019-11-01 南京工业大学 The composite material of a kind of extra small titanium dioxide granule and carbon and its application

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CN102569761A (en) * 2010-12-08 2012-07-11 中国科学院金属研究所 Titanium dioxide/graphene nanocomposite material and preparation method and application thereof
CN104282908A (en) * 2014-09-24 2015-01-14 张五星 Method for synthesizing high-sodium iron-based Prussian blue electrode material
CN104716314A (en) * 2015-03-18 2015-06-17 上海中聚佳华电池科技有限公司 Prussian blue/reduced graphene oxide composite material as well as preparation method and application thereof

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CN102569761A (en) * 2010-12-08 2012-07-11 中国科学院金属研究所 Titanium dioxide/graphene nanocomposite material and preparation method and application thereof
CN104282908A (en) * 2014-09-24 2015-01-14 张五星 Method for synthesizing high-sodium iron-based Prussian blue electrode material
CN104716314A (en) * 2015-03-18 2015-06-17 上海中聚佳华电池科技有限公司 Prussian blue/reduced graphene oxide composite material as well as preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807923A (en) * 2018-06-21 2018-11-13 清远佳致新材料研究院有限公司 The preparation method of sodium-ion battery modifying titanium dioxide-graphene negative material
CN110400702A (en) * 2019-04-15 2019-11-01 南京工业大学 The composite material of a kind of extra small titanium dioxide granule and carbon and its application

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Application publication date: 20170811