CN106848237A - A kind of preparation method of the sodium ion positive electrode of height ratio capacity - Google Patents
A kind of preparation method of the sodium ion positive electrode of height ratio capacity Download PDFInfo
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/36—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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The invention discloses a kind of preparation method of the sodium ion positive electrode of height ratio capacity, it is related to sodium-ion battery field, specifically includes following steps：Prussian blue similar thing material is obtained under certain condition with sodium oxalate, ferrous oxalate, sodium ferrocyanide as raw material first, then bamboo fiber, acetone, Prussian blue similar thing material are well mixed, then it is heat-treated, Prussia's analog material of bamboo charcoal cladding is obtained, it can be used as sodium-ion battery positive material.The stability of material is good, and electric property is excellent, and good cycling stability, high rate performance is excellent, and preparation cost is low.
Description
Technical field：
The present invention relates to sodium-ion battery field, a kind of preparation of the sodium ion positive electrode of height ratio capacity is specifically related to
Method.
Background technology：
Because the reserves of the fuel type energy such as coal and oil are limited and its combustion process has certain influence to environment,
So the clean type energy is increasingly required.Common new energy has solar energy, tide energy and wind energy etc., but these energy are more
With it is discontinuous and unstable the characteristics of, need first to store these energy to solve this problem and utilized again.Grind at present
Relatively broad energy storage device is studied carefully for lithium ion battery, because it has the advantages such as high-energy-density, long-life, but future
Can make lithium resource shortage as the use of extensive energy-storage battery.Sodium element and the element that elemental lithium is same main group, with phase
As property mutually can partly replace, and sodium storage capacity on earth is abundant, with the redox electricity higher than lithium
Position, in price, the aspect such as environmental protection and security is more advantageous.
The maximum challenge that current sodium-ion battery development is subject to is exactly its performance issue, and restricts sodium-ion battery performance
The subject matter of lifting derives from positive electrode.Positive electrode concerns the capacity of battery as the supplier of whole battery sodium source
And cycle performance.The radius ratio lithium ion battery of sodium-ion battery it is big by 30%, so sodium ion insertion and deviate from when need more
Diffusion admittance wide.Moreover the embedding de- process of sodium ion can cause stress irreversible change between larger lattice so that battery is followed
Ring life-span and high rate performance are not as good as lithium ion battery.Three atom mass rate lithiums of sodium are big many, cause the theoretical specific volume of sodium
Amount is not high, and performance is more difficult to surmount lithium ion battery.
Chinese patent (201510616627.4) discloses a kind of preparation method of the vanadium phosphate sodium positive electrode of carbon coating,
Using glucose as reducing agent and carbon source, water is dispersant, by NH4VO3, NaH2PO42H2O and glucose in water ball milling,
By spray drying, after calcining, the vanadium phosphate sodium positive electrode of carbon coating is obtained, it has the structure of homogeneous primary particle,
With the characteristic such as sodium ion diffusion length is short, transmission rate fast, the transmission of high-specific surface area, high conductivity, ion is fast, but the material
The specific capacity of material is not high and high rate performance is poor.
Chinese patent (201610594780.6) discloses a kind of solvent-thermal method and prepares the bar-shaped fluorophosphoric acid Asia of carbon-coated nano
The method of ferrisodium material, it synthesizes Na2FePO4F using ethylene glycol as reaction dissolvent using solvent thermal process, then will
NaFePO4F mixes the fluorophosphoric acid Naferon positive electrode of synthesis carbon coating with glucose, by controlling the species of reaction raw materials,
The technological parameters such as reaction temperature, reaction time, precursor solution pH, you can synthesis Na2FePO4F.Invention Na2FePO4F receives
Rice rod product purity is high, size is small, and draw ratio is high, and good dispersion, specific surface area is big.And a small amount of carbon coating effectively improves positive pole material
The electronic conductivity of material, the energy density using it as the sodium-ion battery of positive electrode is higher.But have in its preparation process
Machine solvent usage amount is big, and high cost, preparation process is numerous and diverse.
The content of the invention：
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of height ratio capacity sodium ion positive electrode system
Preparation Method, the method is simple, low cost, and obtained positive electrode specific capacity is big, and high rate performance is excellent, using it as positive electrode
Sodium-ion battery energy density it is high, good cycle.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of the sodium ion positive electrode of height ratio capacity, comprises the following steps：
(1) by sodium oxalate, ferrous oxalate and deionized water mixing and stirring, obtained solution A；Sodium ferrocyanide and will go
Ionized water mixing and stirring, obtained solution B；
(2) to surfactant is added in solution B, ultrasonic agitation obtains solution C, and by solution A ultrasonic agitation, ultrasound is complete
Solution C is added after finishing, and 30-100h is stirred at 20-30 DEG C, obtain blue precipitate；Blue precipitate obtained above is spent
Ion water washing 4-5 times, is then washed 2-3 times with methyl alcohol, is vacuum dried 12-24h, obtains Prussian blue similar thing material；
(3) by bamboo fiber, acetone mixing and stirring, Prussian blue similar thing material obtained in step (2) is added, and
50-60 DEG C is warming up to, stirring to solvent is volatilized, then ground 300 mesh sieve, the solid that will finally obtain is placed in Muffle furnace
400-500 DEG C, then the lower treatment 50-70min of nitrogen atmosphere protection is warming up to 800-900 DEG C with the heating rate of 10 DEG C/min
Lower treatment 1-3h, cools to room temperature with the furnace, obtains sodium ion positive electrode.
Used as the preferred of above-mentioned technical proposal, in step (1), solution A mesoxalic acid is ferrous, the molar concentration of sodium oxalate is
(0.3-1)mol/L、(0.2-0.9)mol/L。
Used as the preferred of above-mentioned technical proposal, in step (1), the molar concentration of sodium ferrocyanide is 0.75- in solution B
1.5mol/L。
Used as the preferred of above-mentioned technical proposal, in step (2), the surfactant is F127.
Used as the preferred of above-mentioned technical proposal, in step (2), vacuum drying temperature is 100-125 DEG C.
As the preferred of above-mentioned technical proposal, in step (2), before ultrasonic agitation processing solution A, solution A need to be stirred
Mix to clarification.
As the preferred of above-mentioned technical proposal, in step (3), the bamboo fiber, Prussian blue similar thing material, acetone
Amount ratio be 0.1g：(4-6)g：(10-20)ml.
As the preferred of above-mentioned technical proposal, solid is put into when being processed in Muffle furnace first with the intensification speed of 5 DEG C/min
Rate is warming up to 400-500 DEG C.
The present invention is prepared Prussian blue similar using sodium oxalate, ferrous oxalate and sodium ferrocyanide as raw material first
Thing, oxalate and ferrous ion with bit constant are less than ferrous cyanogen root and ferrous ion, using ferrous oxalate as source of iron and Asia
The sodium ferricyanide reacts, and the iron atom allowed in ferrous oxalate slowly release and is coordinated, reasonable adjusting oxalic acid of the present invention with ferrous cyanogen root
Sodium, ferrous oxalate control the speed of growth of Prussian blue similar thing with the amount ratio of sodium ferrocyanide, effectively reduce prepared
The defect of material so that its good stability；
The present invention realizes cladding of the bamboo charcoal to Prussian blue similar thing using bamboo fiber as raw material, so as to improve general Shandong
The electric property of scholar's indigo plant analog；Performance of the selection of the addition, organic solvent of bamboo fiber all to material after cladding has very
Big influence.If bamboo fiber excess, organic solvent can not be completely dissolved it, then influence covered effect；If organic solvent mistake
Amount, not only wastes solvent, can also make solvent volatilization overlong time, increases cost.If bamboo fiber content is too low, prussian blue
It is difficult to be coated completely like thing surface；If bamboo fiber too high levels, the Prussian blue similar composition granule of cladding can be made larger,
Prussian blue similar thing surface is easily set to be exposed again during pulverizing and sieving；The granular size of positive electrode can also influence
Its electric property；Particle is too big, and transmission path of the sodium ion inside positive electrode is more long, influences its de- lithium performance；Particle is too
It is small, the specific surface area of Prussian blue similar thing and tap density can be caused to decline, increase its irreversible capacity.
The invention has the advantages that：
(1) present invention uses cheap sodium oxalate, ferrous oxalate, sodium ferrocyanide as raw material, and reasonable adjusting
The consumption of three simultaneously controls the speed of growth of Prussian blue similar thing so that obtained Prussian blue similar thing defect is few, circulation
Good stability；
(2) present invention realizes that bamboo charcoal coats the preparation of Prussian blue similar thing, bamboo fiber price using bamboo fiber
It is cheap, its excellent in mechanical performance, by reasonable adjusting Carbonization Conditions so that the carbon coated on surface is in cellular, is more improve just
The specific surface area of pole material, obtained positive electrode proportion is small, is more suitable for the requirement of battery lightness；
(3) the obtained positive electrode good cycling stability of the present invention, high rate performance is excellent, using it as the electricity of positive electrode
Pond energy density is big, and capacity is high, and environmental protection, preparation cost is low.
Specific 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 the sodium ion positive electrode of height ratio capacity, comprises the following steps：
(1) by sodium oxalate, ferrous oxalate and deionized water mixing and stirring, obtained solution A；Sodium ferrocyanide and will go
Ionized water mixing and stirring, obtained solution B；Wherein, solution A mesoxalic acid is ferrous, sodium oxalate molar concentration is 0.3mol/L,
0.9mol/L, the molar concentration of sodium ferrocyanide is 0.75mol/L in solution B；
(2) to F127 is added in solution B, ultrasonic agitation obtains solution C, first stirs to clarify solution A, then adopts
Use Solution Under Ultrasound Treatment A, ultrasound that solution C is added after finishing, and 30h is stirred at 20-30 DEG C, obtain blue precipitate；Will be above-mentioned
The blue precipitate for obtaining is washed with deionized 4-5 times, is then washed 2-3 times with methyl alcohol, and 24h is vacuum dried at 100 DEG C, is obtained
Prussian blue similar thing material；
(3) by bamboo fiber, acetone mixing and stirring, Prussian blue similar thing material obtained in step (2) is added, and
Be warming up to 50-60 DEG C, stirring to solvent volatilization, then ground 300 mesh sieve, the solid that will finally obtain be placed in Muffle furnace with
The speed of 5 DEG C/min is warming up to 400 DEG C, and then the lower treatment 50min of nitrogen atmosphere protection is heated up with the heating rate of 10 DEG C/min
1h is processed to 800 DEG C, room temperature is cooled to the furnace, sodium ion positive electrode is obtained；Wherein, the bamboo fiber, Prussian blue
Analog material, the amount ratio of acetone are 0.1g：4g：10ml.
Embodiment 2
A kind of preparation method of the sodium ion positive electrode of height ratio capacity, comprises the following steps：
(1) by sodium oxalate, ferrous oxalate and deionized water mixing and stirring, obtained solution A；Sodium ferrocyanide and will go
Ionized water mixing and stirring, obtained solution B；Wherein, solution A mesoxalic acid is ferrous, sodium oxalate molar concentration is 1mol/L,
0.2mol/L, the molar concentration of sodium ferrocyanide is 1.5mol/L in solution B；
(2) to F127 is added in solution B, ultrasonic agitation obtains solution C, first stirs to clarify solution A, then adopts
Use Solution Under Ultrasound Treatment A, ultrasound that solution C is added after finishing, and 100h is stirred at 20-30 DEG C, obtain blue precipitate；Will be above-mentioned
The blue precipitate for obtaining is washed with deionized 4-5 times, is then washed 2-3 times with methyl alcohol, and 12h is vacuum dried at 125 DEG C, is obtained
Prussian blue similar thing material；
(3) by bamboo fiber, acetone mixing and stirring, Prussian blue similar thing material obtained in step (2) is added, and
Be warming up to 50-60 DEG C, stirring to solvent volatilization, then ground 300 mesh sieve, the solid that will finally obtain be placed in Muffle furnace with
The speed of 5 DEG C/min is warming up to 500 DEG C, and then the lower treatment 50min of nitrogen atmosphere protection is heated up with the heating rate of 10 DEG C/min
1h is processed to 900 DEG C, room temperature is cooled to the furnace, sodium ion positive electrode is obtained；Wherein, the bamboo fiber, Prussian blue
Analog material, the amount ratio of acetone are 0.1g：6g：20ml.
Embodiment 3
A kind of preparation method of the sodium ion positive electrode of height ratio capacity, comprises the following steps：
(1) by sodium oxalate, ferrous oxalate and deionized water mixing and stirring, obtained solution A；Sodium ferrocyanide and will go
Ionized water mixing and stirring, obtained solution B；Wherein, solution A mesoxalic acid ferrous iron, the molar concentration of sodium oxalate are 0.45mol/
L, 0.4mol/L, the molar concentration of sodium ferrocyanide is 1mol/L in solution B；
(2) to F127 is added in solution B, ultrasonic agitation obtains solution C, first stirs to clarify solution A, then adopts
Use Solution Under Ultrasound Treatment A, ultrasound that solution C is added after finishing, and 50h is stirred at 20-30 DEG C, obtain blue precipitate；Will be above-mentioned
The blue precipitate for obtaining is washed with deionized 4-5 times, is then washed 2-3 times with methyl alcohol, and 15h is vacuum dried at 100 DEG C, is obtained
Prussian blue similar thing material；
(3) by bamboo fiber, acetone mixing and stirring, Prussian blue similar thing material obtained in step (2) is added, and
Be warming up to 50-60 DEG C, stirring to solvent volatilization, then ground 300 mesh sieve, the solid that will finally obtain be placed in Muffle furnace with
The speed of 5 DEG C/min is warming up to 400 DEG C, and then the lower treatment 60min of nitrogen atmosphere protection is heated up with the heating rate of 10 DEG C/min
3h is processed to 900 DEG C, room temperature is cooled to the furnace, sodium ion positive electrode is obtained；Wherein, the bamboo fiber, Prussian blue
Analog material, the amount ratio of acetone are 0.1g：4.5g：10ml.
Embodiment 4
A kind of preparation method of the sodium ion positive electrode of height ratio capacity, comprises the following steps：
(1) by sodium oxalate, ferrous oxalate and deionized water mixing and stirring, obtained solution A；Sodium ferrocyanide and will go
Ionized water mixing and stirring, obtained solution B；Wherein, solution A mesoxalic acid is ferrous, sodium oxalate molar concentration is 0.6mol/L,
0.5mol/L, the molar concentration of sodium ferrocyanide is 1.3mol/L in solution B；
(2) to F127 is added in solution B, ultrasonic agitation obtains solution C, first stirs to clarify solution A, then adopts
Use Solution Under Ultrasound Treatment A, ultrasound that solution C is added after finishing, and 60h is stirred at 20-30 DEG C, obtain blue precipitate；Will be above-mentioned
The blue precipitate for obtaining is washed with deionized 4-5 times, is then washed 2-3 times with methyl alcohol, and 15h is vacuum dried at 110 DEG C, is obtained
Prussian blue similar thing material；
(3) by bamboo fiber, acetone mixing and stirring, Prussian blue similar thing material obtained in step (2) is added, and
Be warming up to 50-60 DEG C, stirring to solvent volatilization, then ground 300 mesh sieve, the solid that will finally obtain be placed in Muffle furnace with
The speed of 5 DEG C/min is warming up to 500 DEG C, and then the lower treatment 60min of nitrogen atmosphere protection is heated up with the heating rate of 10 DEG C/min
1h is processed to 800 DEG C, room temperature is cooled to the furnace, sodium ion positive electrode is obtained；Wherein, the bamboo fiber, Prussian blue
Analog material, the amount ratio of acetone are 0.1g：4g：20ml.
Embodiment 5
A kind of preparation method of the sodium ion positive electrode of height ratio capacity, comprises the following steps：
(1) by sodium oxalate, ferrous oxalate and deionized water mixing and stirring, obtained solution A；Sodium ferrocyanide and will go
Ionized water mixing and stirring, obtained solution B；Wherein, solution A mesoxalic acid is ferrous, sodium oxalate molar concentration is 0.8mol/L,
0.5mol/L, the molar concentration of sodium ferrocyanide is 1.5mol/L in solution B；
(2) to F127 is added in solution B, ultrasonic agitation obtains solution C, first stirs to clarify solution A, then adopts
Use Solution Under Ultrasound Treatment A, ultrasound that solution C is added after finishing, and 50h is stirred at 20-30 DEG C, obtain blue precipitate；Will be above-mentioned
The blue precipitate for obtaining is washed with deionized 4-5 times, is then washed 2-3 times with methyl alcohol, and 20h is vacuum dried at 120 DEG C, is obtained
Prussian blue similar thing material；
(3) by bamboo fiber, acetone mixing and stirring, Prussian blue similar thing material obtained in step (2) is added, and
Be warming up to 50-60 DEG C, stirring to solvent volatilization, then ground 300 mesh sieve, the solid that will finally obtain be placed in Muffle furnace with
The speed of 5 DEG C/min is warming up to 500 DEG C, and then the lower treatment 60min of nitrogen atmosphere protection is heated up with the heating rate of 10 DEG C/min
2h is processed to 900 DEG C, room temperature is cooled to the furnace, sodium ion positive electrode is obtained；Wherein, the bamboo fiber, Prussian blue
Analog material, the amount ratio of acetone are 0.1g：5g：15ml.
Embodiment 6
A kind of preparation method of the sodium ion positive electrode of height ratio capacity, comprises the following steps：
(1) by sodium oxalate, ferrous oxalate and deionized water mixing and stirring, obtained solution A；Sodium ferrocyanide and will go
Ionized water mixing and stirring, obtained solution B；Wherein, solution A mesoxalic acid is ferrous, sodium oxalate molar concentration is 0.8mol/L,
0.8mol/L, the molar concentration of sodium ferrocyanide is 1.5mol/L in solution B；
(2) to F127 is added in solution B, ultrasonic agitation obtains solution C, first stirs to clarify solution A, then adopts
Use Solution Under Ultrasound Treatment A, ultrasound that solution C is added after finishing, and 80h is stirred at 20-30 DEG C, obtain blue precipitate；Will be above-mentioned
The blue precipitate for obtaining is washed with deionized 4-5 times, is then washed 2-3 times with methyl alcohol, and 12h is vacuum dried at 120 DEG C, is obtained
Prussian blue similar thing material；
(3) by bamboo fiber, acetone mixing and stirring, Prussian blue similar thing material obtained in step (2) is added, and
Be warming up to 50-60 DEG C, stirring to solvent volatilization, then ground 300 mesh sieve, the solid that will finally obtain be placed in Muffle furnace with
The speed of 5 DEG C/min is warming up to 450 DEG C, and then the lower treatment 70min of nitrogen atmosphere protection is heated up with the heating rate of 10 DEG C/min
2h is processed to 850 DEG C, room temperature is cooled to the furnace, sodium ion positive electrode is obtained；Wherein, the bamboo fiber, Prussian blue
Analog material, the amount ratio of acetone are 0.1g：5g：20ml.
Comparative example 1
Carbon coating step is same as Example 6, and solution A mesoxalic acid is ferrous, careless during prepared by Prussian blue similar thing
The molar concentration of sour sodium is 0.8mol/L, 0.5mol/L, and the molar concentration of sodium ferrocyanide is 2mol/L in solution B.
Comparative example 2
Carbon coating step is same as Example 6, and solution A mesoxalic acid is ferrous, careless during prepared by Prussian blue similar thing
The molar concentration of sour sodium is 0.8mol/L, 1.2mol/L, and the molar concentration of sodium ferrocyanide is 2mol/L in solution B.
Comparative example 3
The preparation of Prussian blue similar thing is identical to embodiment 6, during carbon coating, bamboo fiber, prussian blue
Like thing material, acetone amount ratio be 0.1g：1g：20ml.
Comparative example 4
The preparation of Prussian blue similar thing is identical to embodiment 6, during carbon coating, bamboo fiber, prussian blue
Like thing material, acetone amount ratio be 0.1g：8g：20ml.
Comparative example 5
The preparation of Prussian blue similar thing is identical to embodiment 6, during carbon coating, in Muffle furnace directly with 5 DEG C/
The speed of min is warming up to 850 DEG C, processes 190min.
Comparative example 6
The preparation of Prussian blue similar thing is identical to embodiment 6, during carbon coating, first with 10 in Muffle furnace
DEG C/heating rate of min is warming up to 450 DEG C, the lower treatment 70min of nitrogen atmosphere protection, then with the heating rate of 10 DEG C/min
2h is processed at being warming up to 850 DEG C.
By positive electrode obtained in the present invention and conductive black, binding agent in mass ratio 7:2:Stirred in 1 ratio and stone roller alms bowl
Mix, and add solvent N-methyl pyrilidone in right amount so that material is into uniform sizing material, and is spread evenly across in aluminum foil current collector,
150 μm of thickness is controlled using wet film maker, at least 12h in 80 DEG C of baking oven is then placed into until drying, then in cut-parts
The anode pole piece of diameter 1cm is cut on machine.(the EC with 1mol/LNaPF6/EC+DEC solution as electrolyte:DEC=1:1, volume
Than), or 1mol/L NaPF6/TMS+PTSI solution is electrolyte (TMS:PTSI=95:5, volume ratio), Whatman produces glass
Fiber is barrier film, and hard carbon material produces Labmaster130 type argon gas glove boxes as negative material in German MBRAUN companies
In (H2O<0.1ppm, O2<CR2032 types button cell 0.1ppm) is assembled into case carrying out electrochemical property test.
(1) charge-discharge test
Charge-discharge test generally uses constant current charge-discharge, sets certain current density (mA g-1) tested, the test
Embedding sodium, the removing sodium behavior of active material can be determined, and shows as capacity data and charging and discharging curve, it is possible to obtain forthright again
The performance parameters such as energy, coulombic efficiency, charging and discharging capacity.This experiment uses LAND battery testings, will be assembled before test
Battery standing 12h, and elder generation is used to positive electrode, and in 0.1C constant-current charges, (it is Na that the process is corresponding+The active material of abjection
Material) to 4.0V, then the constant-current discharge (process correspondence Na under the electric current of 0.1C+Embedded active material), it is reduced to 2.0V to voltage
When terminate electric discharge.
(2) cycle life test
This experiment carries out charge-discharge test using CT2001A type LAND battery test system button type batteries, sets electric discharge
To change 0.001V, charge cutoff voltage is 2V to blanking voltage, and setting current density is 60mAg-1, cycle-index is 50 times.
Test result is as shown in the table：
| Specific discharge capacity under 0.1C electric currents, mAh/g | 50 capacity, mAh/g are circulated under 0.1C | |
| Embodiment 1 | 180.5 | 180.1 |
| Embodiment 2 | 179.3 | 179.3 |
| Embodiment 3 | 181.5 | 180.9 |
| Embodiment 4 | 178.6 | 178.2 |
| Embodiment 5 | 179.2 | 179.0 |
| Embodiment 6 | 181.7 | 181.0 |
| Comparative example 1 | 150.4 | 96.5 |
| Comparative example 2 | 151.3 | 111.1 |
| Comparative example 3 | 167.8 | 130.2 |
| Comparative example 4 | 165.5 | 101.5 |
| Comparative example 5 | 175.5 | 120.9 |
| Comparative example 6 | 179.6 | 155.5 |
The consumption that the present invention passes through sodium oxalate, ferrous oxalate, sodium ferrocyanide is can be seen that from the data in above table
Than so that the cyclical stability of obtained Prussian blue similar thing is more excellent；During carbon coating, reasonable adjusting of the present invention
The consumption of bamboo fiber and Prussian blue similar thing so that obtained positive electrode specific capacity is high, and electric property is good, the bar of carbonization
Part also has a great impact to the performance of positive electrode, and the present invention is warming up to 400-500 DEG C with the heating rate of 5 DEG C/min first
Treatment carries out pre- carbonization, and the speed of growth of crystal grain, is then warming up to the heating rate of 10 DEG C/min effectively after control carbonization
800-900 DEG C for the treatment of so that the material crystalline degree after carbonization is good, it is mesoporous uniform, it is uniform with Prussian blue similar thing Surface coating,
Excellent bonding performance.
Claims (8)
1. the preparation method of the sodium ion positive electrode of a kind of height ratio capacity, it is characterised in that comprise the following steps：
(1) by sodium oxalate, ferrous oxalate and deionized water mixing and stirring, obtained solution A；By sodium ferrocyanide and deionization
Water mixing and stirring, obtained solution B；
(2) to surfactant is added in solution B, ultrasonic agitation obtains solution C, by solution A ultrasonic agitation, after ultrasound is finished
Solution C is added, and 30-100h is stirred at 20-30 DEG C, obtain blue precipitate；By blue precipitate deionization obtained above
Water washing 4-5 times, is then washed 2-3 times with methyl alcohol, is vacuum dried 12-24h, obtains Prussian blue similar thing material；
(3) by bamboo fiber, acetone mixing and stirring, Prussian blue similar thing material obtained in step (2) is added, and heat up
To 50-60 DEG C, stirring to solvent is volatilized, then ground 300 mesh sieve, and the solid that will finally obtain is placed in Muffle furnace in 400-
500 DEG C, the lower treatment 50-70min of nitrogen atmosphere protection locates at being then warming up to 800-900 DEG C with the heating rate of 10 DEG C/min
Reason 1-3h, cools to room temperature with the furnace, obtains sodium ion positive electrode.
2. the preparation method of the sodium ion positive electrode of a kind of height ratio capacity as claimed in claim 1, it is characterised in that：Step
(1) in, solution A mesoxalic acid is ferrous, the molar concentration of sodium oxalate is (0.3-1) mol/L, (0.2-0.9) mol/L.
3. the preparation method of the sodium ion positive electrode of a kind of height ratio capacity as claimed in claim 1, it is characterised in that：Step
(1) in, the molar concentration of sodium ferrocyanide is 0.75-1.5mol/L in solution B.
4. the preparation method of the sodium ion positive electrode of a kind of height ratio capacity as claimed in claim 1, it is characterised in that：Step
(2) in, the surfactant is F127.
5. the preparation method of the sodium ion positive electrode of a kind of height ratio capacity as claimed in claim 1, it is characterised in that：Step
(2) in, vacuum drying temperature is 100-125 DEG C.
6. the preparation method of the sodium ion positive electrode of a kind of height ratio capacity 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. the preparation method of the sodium ion positive electrode of a kind of height ratio capacity as claimed in claim 1, it is characterised in that：Step
(3) in, the bamboo fiber, Prussian blue similar thing material, the amount ratio of acetone are 0.1g：(4-6)g：(10-20)ml.
8. the preparation method of the sodium ion positive electrode of a kind of height ratio capacity as claimed in claim 1, it is characterised in that：Will be solid
Body is put into when processing in Muffle furnace and is warming up to 400-500 DEG C with the heating rate of 5 DEG C/min first.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109950613A (en) * | 2019-04-22 | 2019-06-28 | 辽宁星空钠电电池有限公司 | A kind of sodium-ion battery with superior low-temperature performance |
| CN112151804A (en) * | 2020-09-27 | 2020-12-29 | 广州大学 | Prussian blue analogue-based carbon-coated transition metal oxide and preparation method and application thereof |
| CN113479911A (en) * | 2021-06-21 | 2021-10-08 | 华中科技大学 | Iron-based Prussian blue, preparation method and application thereof |
| CN114335518A (en) * | 2017-10-30 | 2022-04-12 | 宁德时代新能源科技股份有限公司 | Positive active material, preparation method thereof and sodium ion battery |
| CN114956121A (en) * | 2022-06-20 | 2022-08-30 | 郑州轻工业大学 | High-crystallization Prussian blue analogue material and preparation method and application thereof |
-
2017
- 2017-02-22 CN CN201710095574.5A patent/CN106848237A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114335518A (en) * | 2017-10-30 | 2022-04-12 | 宁德时代新能源科技股份有限公司 | Positive active material, preparation method thereof and sodium ion battery |
| CN109950613A (en) * | 2019-04-22 | 2019-06-28 | 辽宁星空钠电电池有限公司 | A kind of sodium-ion battery with superior low-temperature performance |
| CN112151804A (en) * | 2020-09-27 | 2020-12-29 | 广州大学 | Prussian blue analogue-based carbon-coated transition metal oxide and preparation method and application thereof |
| CN113479911A (en) * | 2021-06-21 | 2021-10-08 | 华中科技大学 | Iron-based Prussian blue, preparation method and application thereof |
| CN114956121A (en) * | 2022-06-20 | 2022-08-30 | 郑州轻工业大学 | High-crystallization Prussian blue analogue material and preparation method and application thereof |
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Application publication date: 20170613 |