CN104953172A - Sodium-ion battery cathode materials, preparation method of sodium-ion battery cathode materials, and sodium-ion batteries - Google Patents
Sodium-ion battery cathode materials, preparation method of sodium-ion battery cathode materials, and sodium-ion batteries Download PDFInfo
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- CN104953172A CN104953172A CN201510443516.8A CN201510443516A CN104953172A CN 104953172 A CN104953172 A CN 104953172A CN 201510443516 A CN201510443516 A CN 201510443516A CN 104953172 A CN104953172 A CN 104953172A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
- 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 provides sodium-ion battery cathode materials, a preparation method of the sodium-ion battery cathode materials, and sodium-ion batteries. The composition of the cathode material A is Na(Na(x)Fe(1-x-y-z)Ni(y)Mn(z))O2, wherein x is greater than 0 and less than or equal to 0.2, y is greater than 0 and less than 0.4, and z is greater than 0 and less than 0.4. The preparation method comprises the following steps: mixing a precursor and sodium salt, sintering, and cooling. The cathode material B is formed by coating the surface of the cathode material A with a layer of aluminium oxide. The invention further provides the sodium-ion battery A or B, the anode of the sodium-ion battery A or B is correspondingly made of the cathode material A or B. The preparation method for the cathode material A or B is simple in process and easy to be produced in large scale; the cathode materials A and B are good in consistency, have high specific capacity and better rate capability, and give consideration to the charge-discharge cycling stability, so as to improve the electrochemical performance and the energy density of the sodium-ion batteries and facilitate the practical development of the sodium-ion batteries.
Description
Technical field
The present invention is specifically related to sodium-ion battery positive material A, B, and preparation method thereof, sodium-ion battery.
Background technology
The secondary cell system being suitable for extensive stored energy application must have that resource is extensive, cheap, environmental friendliness, safe and reliable feature, takes into account the chemical property such as energy density, power density index request simultaneously.Therefore, development can meet these energy-storage battery systems required is important technical challenges that material and energy field face.
Although lithium ion battery has excellent chemical property, its high cost, poor stability.Consider from aspects such as performance, cost, environment, sodium-ion battery green, safety, cheapness, as stored energy application, there is very large advantage, the battery development limitation problem because lithium resource shortage causes can be relaxed to a great extent, cause researcher's interest widely in recent years.
Although sodium ion can bring series of advantages, also there is many stubborn problems, such as, the ionic radius of sodium is large, and alternative positive and negative pole material system is very limited.At present, the positive electrode of the applicable sodium-ion battery application of having developed comprises vanadium phosphate sodium, the binary of Prussian blue, sodium manganate, sodium vanadate, sodium or ternary oxide, the ternary material wherein comprising nickel-iron-manganese presents best comprehensive electrochemical, greatly reducing tertiary cathode material cost by adding of iron, is one of first-selected positive electrode of sodium-ion battery of future generation.The NaNi that document reported first (Electrochemistry Communications, 18,2012,66-69) adopts coprecipitation to prepare
1/3fe
1/3mn
1/3o
2positive electrode first circle discharge capacity reaches 123mAh/g, show that this positive electrode has good cyclical stability, but first circle coulombic efficiency is lower by full battery testing, needs to improve further in preparation technology.NaNi
1/3co
1/3mn
1/3o
2positive electrode (Electrochemistry Communications, 38,2014,79-81) presents the specific capacity of 150mAh/g, but due to cobalt-containing materials, its high expensive, is not suitable for applying in extensive energy-storage battery.Chinese patent CN104505507A discloses the NaFeO of a seed ginseng Ti
2-NaNiO
2binary positive material, by mixing Ti, improves the stability of material, but its discharge capacity of showing only has 110mAh/g.Chinese patent CN102522553A discloses a kind of transient metal complex positive electrode of three-dimensional frame structure, present excellent cyclical stability, but the 1C multiplying power discharge capacity of this positive electrode only has 78mAh/g.Therefore, how at the charging and discharging capacity improving material, and the cyclical stability taking into account positive electrode just becomes one of challenge in the research of current sodium-ion battery.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defect that in prior art, sodium-ion battery positive material charging and discharging capacity and cyclical stability can not improve simultaneously, provide sodium-ion battery positive material A, B, and preparation method thereof, sodium-ion battery.Preparation method's technique of sodium-ion battery positive material A of the present invention, B is simple, is easy to accomplish scale production.Sodium-ion battery positive material A prepared by the present invention, B, consistency is good, while having height ratio capacity, preferably high rate performance, also takes into account charge and discharge cycles stability, thus promote chemical property and the energy density of sodium-ion battery, be conducive to the practical exploitation of sodium-ion battery.In addition, in sodium-ion battery positive material A of the present invention, B, iron content can more than 50%, and while greatly reducing costs, its performance is not affected substantially.
The present invention solves the problems of the technologies described above by the following technical programs.
The invention provides a kind of sodium-ion battery positive material A, described sodium-ion battery positive material A consists of Na (Na
xfe
1-x-y-zni
ymn
z) O
2, wherein 0<x≤0.2,0<y<0.4,0<z<0.4.
In the present invention, described x is preferably 0.05≤x≤0.2, is more preferably 0.05≤x≤0.1, is 0.05,0.1 or 0.2 best.
In the present invention, described y is preferably 0.1,0.2,0.25 or 0.3.
In the present invention, described z is preferably 0.1,0.2 or 0.3.
In the present invention, the composition of described sodium-ion battery positive material A is preferably Na (Na
0.1fe
0.5ni
0.2mn
0.2) O
2, Na (Na
0.05fe
0.4ni
0.25mn
0.3) O
2, Na (Na
0.1fe
0.3ni
0.3mn
0.3) O
2or Na (Na
0.2fe
0.6ni
0.1mn
0.1) O
2.
Present invention also offers a kind of sodium-ion battery positive material B, described sodium-ion battery positive material B is the Surface coating one deck aluminium oxide at described sodium-ion battery positive material A.
In the present invention, the covering amount of described aluminium oxide is the covering amount that field of lithium ion battery routine uses, the present invention is preferably 0.5-2%, and more preferably 0.5%, 1.0% or 2.0%, described percentage is the mass percent of alumina phase for sodium-ion battery positive material B.
Present invention also offers the preparation method of a kind of described sodium-ion battery positive material A, it comprises the steps: presoma and sodium salt mixing, sintering, and cooling, obtains sodium-ion battery positive material A;
Wherein, described presoma is the solid obtained by the mixed aqueous solution of nickel salt, molysite and manganese salt, precipitation reagent and complexing agent hybrid reaction; The molar ratio of nickle atom, iron atom and manganese atom is y:(1-x-y-z): z, mole total amount sum of nickle atom, iron atom and manganese atom and the molar ratio of sodium atom are (1-x): (1+x), 0<x≤0.2,0<y<0.4,0<z<0.4.
In the present invention, described x is preferably 0.05≤x≤0.2, is more preferably 0.05≤x≤0.1, is 0.05,0.1 or 0.2 best.
In the present invention, described y is preferably 0.1,0.2,0.25 or 0.3.
In the present invention, described z is preferably 0.1,0.2 or 0.3.
In the present invention, the composition of described sodium-ion battery positive material A is preferably Na (Na
0.1fe
0.5ni
0.2mn
0.2) O
2, Na (Na
0.05fe
0.4ni
0.25mn
0.3) O
2, Na (Na
0.1fe
0.3ni
0.3mn
0.3) O
2or Na (Na
0.2fe
0.6ni
0.1mn
0.1) O
2.
In the present invention, the water in described mixed aqueous solution is preferably deionized water.
In the present invention, described nickel salt is the nickel salt that sodium-ion battery positive material field routine uses, and is preferably selected from one or more in nickelous sulfate, nickel chloride and nickel nitrate, more preferably nickelous sulfate.
In the present invention, described molysite is the conventional divalent iron salt in sodium-ion battery positive material field, is preferably selected from ferrous sulfate and/or frerrous chloride, more preferably ferrous sulfate.
In the present invention, described manganese salt is the manganese salt that sodium-ion battery positive material field routine uses, and is preferably selected from one or more in manganese sulfate, manganese chloride and manganese nitrate, more preferably manganese sulfate.
In the present invention, the concentration of described mixed aqueous solution is conventional in this area, and being preferably 1-2mol/L, is more preferably 1mol/L or 2mol/L.
In the present invention, described precipitation reagent is the precipitation reagent that sodium-ion battery positive material field routine uses, and is preferably the aqueous solution of NaOH.The concentration of described precipitation reagent is conventional in this area, and being preferably 1-5mol/L, is more preferably 1mol/L, 2mol/L, 4mol/L or 5mol/L.
In the present invention, described complexing agent is the complexing agent that sodium-ion battery positive material field routine uses, and is preferably the aqueous solution of ammoniacal liquor.The concentration of described complexing agent is conventional in this area, and being preferably 1-5mol/L, being more preferably, is more preferably 1mol/L, 2mol/L, 4mol/L or 5mol/L.
In the present invention, described presoma is preferably by by described mixed aqueous solution, described precipitation reagent and described complexing agent and stream adds the solid carrying out hybrid reaction acquisition in reactor.
Wherein, the temperature of described reaction is that this area is conventional, and being preferably 40-60 DEG C, is more preferably 40 DEG C, 50 DEG C or 60 DEG C.The time of described reaction is that this area is conventional, and being preferably 5-10 hour, is more preferably 5 hours, 8 hours or 10 hours.The pH value of described reaction is that this area is conventional, and being preferably 9.0-11.5, is more preferably 9.0,10.5 or 11.5.The mixing speed of described reactor is conventional in this area, and being preferably 400-800r/min, is more preferably 400r/min, 500r/min or 800r/min.The flow that mixed aqueous solution adds reactor is the flow of sodium-ion battery positive material field mixed aqueous solution routine when preparing presoma, and being preferably 6-200mL/min, is more preferably 8mL/min, 10mL/min, 100mL/min or 200mL/min.The flow that precipitation reagent adds reactor is the flow of sodium-ion battery positive material field precipitation reagent routine when preparing presoma, and being preferably 4-100mL/min, is more preferably 4mL/min, 40mL/min or 100mL/min.The flow that complexing agent adds reactor is the flow of sodium-ion battery positive material field complexing agent routine when preparing presoma, and being preferably 4-100mL/min, is more preferably 4mL/min, 40mL/min or 100mL/min.
In the present invention, preferably, before presoma and sodium salt mixing, the reactant liquor by the mixed aqueous solution of nickel salt, molysite and manganese salt, precipitation reagent and complexing agent hybrid reaction is first carried out ageing, filters, washing, dry, obtain precursor powder.
Wherein, described ageing is routine operation in this area, preferably for leaving standstill 11-13 hour, more preferably for leaving standstill 12 hours.Describedly be filtered into this area routine operation.Described washing is this area routine operation, preferably adopts deionized water to wash.The number of times of described washing is that this area is conventional, is preferably twice.Described drying is this area routine operation, is preferably 95-103 DEG C and dries 9-11 hour, is more preferably 100 DEG C and dries 10 hours.
In the present invention, described sodium salt is the sodium salt that sodium-ion battery positive material field routine uses, and is preferably selected from one or more in sodium carbonate, sodium nitrate and sodium acetate.
In the present invention, the atmosphere of described sintering is routine operation in this area, is preferably air atmosphere.The temperature of described sintering is conventional in this area, and being preferably 600-1000 DEG C, is more preferably 600 DEG C, 700 DEG C, 850 DEG C or 950 DEG C.The time of described sintering is the sintering operation of sodium-ion battery positive material field routine, is preferably 10-20 hour, is more preferably 10 hours, 15 hours or 20 hours.
In the present invention, described cooling be operating as this area routine, preferably for naturally cooling to room temperature.
Present invention also offers a kind of sodium-ion battery positive material A obtained by above-mentioned preparation method.
Present invention also offers a kind of sodium-ion battery A, its positive pole comprises described sodium-ion battery positive material A.
Present invention also offers the preparation method of a kind of described sodium-ion battery positive material B, it comprises the steps: the Surface coating one deck aluminium oxide at described sodium-ion battery positive material A, obtains sodium-ion battery positive material B.
In the present invention, in described sodium-ion battery positive material B, the covering amount of aluminium oxide is the covering amount that field of lithium ion battery routine uses, the present invention is preferably 0.5-2%, more preferably 0.5%, 1.0% or 2.0%, described percentage is the mass percent of alumina phase for sodium-ion battery positive material B.
In the method being operating as the coated aluminum oxide that field of lithium ion battery routine is selected of Surface coating one deck aluminium oxide of described sodium-ion battery positive material A, preferably, carry out in the steps below: in water, by described sodium-ion battery positive material A and the mixing of aluminium salt, after the granulation of gained mixed liquor drying, heat treatment, obtains sodium-ion battery positive material B.
Wherein, described aluminium salt is the aluminium salt that field of lithium ion battery anode routine uses, and is preferably selected from aluminum nitrate and/or aluminum acetate.Described mixing preferably mixes in ultrasonic mode.The described ultrasonic time is that this area is conventional, and being preferably 5-15 minute, is more preferably 5 minutes, 10 minutes or 15 minutes.Described ultrasonic temperature is conventional in this area, is preferably 20-30 DEG C, is more preferably 25 DEG C.
Wherein, preferably, adopt measuring pump to be transported to spray dryer described mixed liquor and carry out spray drying granulation.The charging rate of described measuring pump is conventional in this area, and being preferably 2-10mL/min, is more preferably 2mL/min or 10mL/min.The inlet temperature of described spray dryer is that this area is conventional, and being preferably 200-250 DEG C, is more preferably 200 DEG C, 210 DEG C, 230 DEG C or 250 DEG C.The outlet temperature of described spray dryer is that this area is conventional, and being preferably 100-120 DEG C, is more preferably 100 DEG C, 110 DEG C or 120 DEG C.
Wherein, described heat treatment is that aluminium reactant salt is converted to the routine operation of aluminium oxide by field of lithium ion battery, preferably heat-treat at granulation gained sample is placed in 300-450 DEG C, more preferably at granulation gained sample is placed in 300-450 DEG C, heat-treat 1-2 hour, best for the sample of granulation gained is placed in Muffle furnace, at 300-450 DEG C, heat-treat 1-2 hour.
Wherein, preferably, carry out after heat treatment being cooled to room temperature.Described is cooled to this area routine, preferably for naturally cooling.
Present invention also offers a kind of sodium-ion battery positive material B obtained by above-mentioned preparation method.
Present invention also offers a kind of sodium-ion battery B, its positive pole comprises described sodium-ion battery positive material B.
On the basis meeting this area general knowledge, above-mentioned each optimum condition, can combination in any, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is:
1, sodium-ion battery positive material A of the present invention, B are rich sodium system, and sodium ion in the metal layer and manganese ion construct microstructure sodium manganate Na
2mnO
3, and form solid solution with agent structure, in initial charge process, activate into manganese oxide, can discharge more sodium ion, this part deintercalation sodium ion out significantly increases the charging and discharging capacity of material, improves the energy density of sodium-ion battery positive material; Also take into account charge and discharge cycles stability simultaneously, thus promote the chemical property of sodium-ion battery, be conducive to the practical exploitation of sodium-ion battery.Nickel oxide iron sodium manganate positive electrode (comparative example 1) in prior art of comparing in sodium-ion battery, the specific capacity (i.e. first circle discharge capacity increase rate) of the sodium-ion battery positive material A prepared by the present invention, B, first circle discharge and recharge coulombic efficiency are all improved significantly.
In addition, between the positive electrode that the present invention produces at every turn, deviation is little, consistency, reproducible; In sodium-ion battery positive material A or B, iron content can more than 50%, and while greatly reducing costs, its performance is not affected substantially.
Sodium-ion battery positive material A of the present invention, B all can be applicable to prepare sodium-ion battery.Sodium-ion battery is compared lithium ion battery, and green, safety, cheapness, have very large advantage as stored energy application.
2, the present invention can adopt liquid-phase coprecipitation to prepare presoma, presoma powder can well be prepared according to stoichiometric equation, avoid metal ion mixing that conventional solid ball-milling technology causes uneven and affect the specific capacity of positive electrode and the defect of cyclical stability.The present invention is at Surface coating one deck aluminium oxide of sodium-ion battery positive material A, form sodium-ion battery positive material B, the contact of further reduction positive electrode B and electrolyte, thus the comprehensive electrochemical such as cycle performance, high rate performance, high temperature performance improving sodium-ion battery.Compare liquid-coating method, adopting drying process with atomizing to carry out coated aluminum oxide can better improve the coated uniformity.
Preparation method's technique of sodium-ion battery positive material A of the present invention, B is simple, is easy to accomplish scale production.
Accompanying drawing explanation
Fig. 1 is the charging and discharging curve figure of sodium-ion battery positive material B under 26mA/g current density that embodiment 1 obtains.
Fig. 2 is the charge-discharge test curve chart of material under 26mA/g current density of embodiment 1 sodium-ion battery positive material A, comparative example 1, wherein, Ia and Ib is respectively the charging and discharging curve of sodium-ion battery positive material A, IIa and IIb is respectively the charging and discharging curve of the material of comparative example 1.
Fig. 3 is the cycle performance test curve figure of the sodium-ion battery positive material B that embodiment 1 obtains.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
Embodiment 1
1, the preparation method of sodium-ion battery positive material A
(1) weigh nickelous sulfate, ferrous sulfate and manganese sulfate successively, make the molar ratio of nickle atom, iron atom and manganese atom be 0.2:0.5:0.2, weighing sodium carbonate, makes (n
fe+ n
mn+n
ni): n
na=1:1.1;
Employing deionized water is dispersant, and soluble transition metal salt is mixed with the mixed aqueous solution that concentration is 1mol/L, NaOH is mixed with the precipitation reagent that concentration is 5mol/L, ammoniacal liquor is mixed with the complexing agent that concentration is 5mol/L;
(2) by mixed aqueous solution, precipitation reagent and complexing agent simultaneously and stream adds in reactor, after carrying out coprecipitation reaction, rear ageing leaves standstill 12h, filtration, deionized water wash 2 times, 100 DEG C dries 10h and obtains precursor powder; After precursor powder and sodium carbonate Homogeneous phase mixing, in the lower 850 DEG C of sintering 15h of air atmosphere, naturally cool, obtain sodium-ion battery positive material A, it consists of Na (Na
0.1fe
0.5ni
0.2mn
0.2) O
2;
Wherein, the mixing speed of reactor is 500r/min, and the temperature of coprecipitation reaction is 50 DEG C, and the coprecipitation reaction time is 8h, and the pH value of coprecipitation reaction is 11.5; The flow that mixed aqueous solution, precipitation reagent and complexing agent enter reactor is respectively 10mL/min, 4mL/min and 4mL/min.
2, the preparation method of sodium-ion battery positive material B
At 20 DEG C, above-mentioned sodium-ion battery positive material A and aluminum nitrate are joined deionized water for ultrasonic dispersion 15min, be transported to spray dryer by measuring pump with the charging rate of 2mL/min and carry out spray drying granulation; The inlet temperature of spray dryer is 210 DEG C, and outlet temperature is 110 DEG C; The powder sample having made grain is placed in Muffle furnace in 450 DEG C of heat treatment 2h, obtain sodium-ion battery positive material B, it consists of Na (Na
0.1fe
0.5ni
0.2mn
0.2) O
2/ Al
2o
3.
Wherein, alumina-coated amount 0.5%, described percentage is the mass percent of alumina phase for sodium-ion battery positive material B.
Embodiment 2
1, the preparation method of sodium-ion battery positive material A
(1) weigh nickel nitrate, ferrous sulfate and manganese nitrate successively, the molar ratio making nickle atom, iron atom and manganese atom is 0.25:0.4:0.3, takes sodium acetate, makes (n
fe+ n
mn+n
ni): n
na=1:1.05;
Employing deionized water is dispersant, and soluble transition metal salt is mixed with the mixed aqueous solution that concentration is 2mol/L, NaOH is mixed with the precipitation reagent that concentration is 5mol/L, ammoniacal liquor is mixed with the complexing agent that concentration is 5mol/L;
(2), by mixed aqueous solution, precipitation reagent and complexing agent and after stream adds and carry out coprecipitation reaction in reactor, rear ageing 12h, filtration, deionization wash 2 times, 100 DEG C dries 10h and obtains precursor powder; After precursor powder and sodium acetate Homogeneous phase mixing, in the lower 950 DEG C of sintering 10h of air atmosphere, naturally cool, obtain sodium-ion battery positive material A, it consists of Na (Na
0.05fe
0.4ni
0.25mn
0.3) O
2.
Wherein, the mixing speed of reactor is 800r/min, and the temperature of coprecipitation reaction is 40 DEG C, and the coprecipitation reaction time is 10h, and the pH value of coprecipitation reaction is 10.5; The flow that mixed aqueous solution, precipitation reagent and complexing agent enter reactor is respectively 100mL/min, 40mL/min and 40mL/min.
2, the preparation method of sodium-ion battery positive material B
At 20 DEG C, above-mentioned sodium-ion battery positive material A and aluminum acetate are joined deionized water for ultrasonic dispersion 15min, be transported to spray dryer by measuring pump with the charging rate of 2mL/min and carry out spray drying granulation; The inlet temperature of spray dryer is 230 DEG C, and outlet temperature is 120 DEG C; The powder sample having made grain is placed in Muffle furnace in 350 DEG C of heat treatment 2h, obtain sodium-ion battery positive material B, it consists of Na (Na
0.05fe
0.4ni
0.25mn
0.3) O
2/ Al
2o
3.
Wherein, alumina-coated amount 1.0%, described percentage is the mass percent of alumina phase for sodium-ion battery positive material B.
Embodiment 3
1, the preparation method of sodium-ion battery positive material A
(1) weigh nickel chloride, frerrous chloride and manganese chloride successively, make the molar ratio of nickle atom, iron atom and manganese atom be 0.3:0.3:0.3, weighing sodium carbonate, makes (n
fe+ n
mn+n
ni): n
na=1:1.1;
Employing deionized water is dispersant, and soluble transition metal salt is mixed with the mixed aqueous solution that concentration is 1mol/L, NaOH is mixed with the precipitation reagent that concentration is 2mol/L, ammoniacal liquor is mixed with the complexing agent that concentration is 2mol/L;
(2), by mixed aqueous solution, precipitation reagent and complexing agent and after stream adds and carry out coprecipitation reaction in reactor, rear ageing leaves standstill 12h, filtration, deionized water wash twice, 100 DEG C dry 10h and obtain precursor powder; After precursor powder and sodium carbonate Homogeneous phase mixing, in the lower 700 DEG C of sintering 15h of air atmosphere, naturally cool, obtain sodium-ion battery positive material A, it consists of Na (Na
0.1fe
0.3ni
0.3mn
0.3) O
2;
Wherein, the mixing speed of reactor is 400r/min, and the temperature of coprecipitation reaction is 60 DEG C, and the coprecipitation reaction time is 5h, and the pH value of coprecipitation reaction is 11.5; The flow that mixed aqueous solution, precipitation reagent and complexing agent enter reactor is respectively 8mL/min, 4mL/min and 4mL/min.
2, the preparation method of sodium-ion battery positive material B
At 20 DEG C, above-mentioned sodium-ion battery positive material A and aluminum nitrate are joined deionized water for ultrasonic dispersion 10min, be transported to spray dryer by measuring pump with the charging rate of 2mL/min and carry out spray drying granulation; The inlet temperature of spray dryer is 200 DEG C, and outlet temperature is 110 DEG C; The powder sample having made grain is placed in Muffle furnace in 400 DEG C of heat treatment 1h, obtain sodium-ion battery positive material B, it consists of Na (Na
0.1fe
0.3ni
0.3mn
0.3) O
2/ Al
2o
3.
Wherein, alumina-coated amount 2.0%, described percentage is the mass percent of alumina phase for sodium-ion battery positive material B.
Embodiment 4
1, the preparation method of sodium-ion battery positive material A
(1) weigh nickelous sulfate, ferrous sulfate and manganese sulfate successively, make the molar ratio of nickle atom, iron atom and manganese atom be 0.1:0.6:0.1, weighing sodium carbonate, makes (n
fe+ n
mn+n
ni): n
na=1:1.2;
Employing deionized water is dispersant, and soluble transition metal salt is mixed with the mixed aqueous solution that concentration is 1mol/L, NaOH is mixed with the precipitation reagent that concentration is 4mol/L, ammoniacal liquor is mixed with the complexing agent that concentration is 4mol/L;
(2), by mixed aqueous solution, precipitation reagent and complexing agent and after stream adds and carry out coprecipitation reaction in reactor, rear ageing leaves standstill 12h, filtration, deionized water wash twice, 100 DEG C dry 10h and obtain precursor powder; After precursor powder and sodium carbonate Homogeneous phase mixing, in the lower 600 DEG C of sintering 20h of air atmosphere, naturally cool, obtain sodium-ion battery positive material, it consists of Na (Na
0.2fe
0.6ni
0.1mn
0.1) O
2;
Wherein, the mixing speed of reactor is 800r/min, and the temperature of coprecipitation reaction is 50 DEG C, and the coprecipitation reaction time is 10h, and the pH value of coprecipitation reaction is 9.0; The flow that mixed aqueous solution, precipitation reagent and complexing agent enter reactor is respectively 200mL/min, 100mL/min and 100mL/min.
2, the preparation method of sodium-ion battery positive material B
At 25 DEG C, above-mentioned sodium-ion battery positive material and aluminum nitrate are joined deionized water for ultrasonic dispersion 5min, be transported to spray dryer by measuring pump with the charging rate of 10mL/min and carry out spray drying granulation; The inlet temperature of spray dryer is 250 DEG C, and outlet temperature is 100 DEG C; The powder sample having made grain is placed in Muffle furnace in 300 DEG C of heat treatment 1h, obtain sodium-ion battery positive material B, it consists of Na (Na
0.2fe
0.6ni
0.1mn
0.1) O
2/ Al
2o
3.
Wherein, alumina-coated amount 0.5%, described percentage is the mass percent of alumina phase for sodium-ion battery positive material B.
Comparative example 1
According to Electrochemistry Communications, the 18,2012, the 67th page, disclosed in the 1st section, left hurdle, preparation method prepares nickel oxide iron sodium manganate positive electrode, and it consists of NaNi
1/3fe
1/3mn
1/3o
2.
Effect example 1
The sodium-ion battery positive material (sodium-ion battery positive material namely on non-coated aluminum oxide) embodiment 1 prepared carries out ICP test, and its test result is as shown in table 1.Wherein, ICP model is the iCAP 6000Radial of Thermo Fischer Scient Inc..As shown in Table 1, the composition Na (Na of ICP test result and sodium-ion battery positive material of the present invention
0.1fe
0.5ni
0.2mn
0.2) O
2match.
Table 1
In like manner, the sodium-ion battery positive material prepared by embodiment 2-4 carries out ICP test, and composition and its ICP test result of the sodium-ion battery positive material of each embodiment all match.
Effect example 2
Take alumina-coated sodium-ion battery positive material prepared by 1.8g embodiment 1, add 0.1g carbon black and 0.1g is dissolved in N, the Kynoar of N '-methyl pyrrolidone, be coated on after mixing on aluminium foil and make electrode slice.In the glove box of argon gas atmosphere, be to electrode with sodium metal sheet, Celgard2700 is barrier film, 1M/NaClO
4/ PC:EMC (1:1) is electrolyte, is assembled into button cell.
In 2.0-4.0V voltage range, charge-discharge test is carried out to battery.Fig. 1 is the charge-discharge test curve chart of embodiment 1 alumina-coated sodium-ion battery positive material under 26mA/g current density.
The button cell of embodiment 1 sodium-ion battery positive material A and comparative example 1 nickel oxide iron sodium manganate positive electrode is made according to method described above.Fig. 2 is the charge-discharge test curve chart of material under 26mA/g current density of embodiment 1 sodium-ion battery positive material A, comparative example 1, wherein, Ia and Ib is respectively the charging and discharging curve of sodium-ion battery positive material A, IIa and IIb is respectively the charging and discharging curve of the material of comparative example 1.
The button cell of embodiment 2,3 sodium-ion battery positive material A, B is made, the charge-discharge test under 26mA/g current density according to method described above.For ease of comparing, by embodiment 1-3, comparative example 1 survey data list 2, as follows.
Table 2
In like manner, embodiment 4 gained sodium-ion battery positive material A, B and embodiment 1-3 are similar, have higher first circle discharge capacity and first circle discharge and recharge coulombic efficiency under the current density of 26mA/g.
In addition, when current density reaches 130mA/g, the first circle discharge capacity of sodium-ion battery positive material B prepared by embodiment 1 reaches 121mAh/g, presents higher specific discharge capacity.Fig. 3 is the cycle performance of sodium-ion battery positive material B battery when current density is 130mA/g prepared by embodiment 1, and after 50 cycle periods, battery capacity conservation rate is more than 90%.
Make the button cell of embodiment 2 sodium-ion battery positive material B according to method described in embodiment 1, sodium sheet be to electrode, and under 130mA/g current density, after circulation 50 times, capability retention is 88%.Make the button cell of embodiment 3 sodium-ion battery positive material B according to method described in embodiment 1, sodium sheet be to electrode, and under 130mA/g current density, after circulation 50 times, capability retention is 93%.Sodium-ion battery positive material prepared by embodiment 4 also has higher charge/discharge capacity, high rate performance and cyclical stability.For ease of comparing, above-mentioned data are listed in table 3, as follows:
Table 3
In like manner, embodiment 4 gained sodium-ion battery positive material A, B and embodiment 1-3 are similar, have higher first circle discharge capacity and battery capacity conservation rate under the current density of 130mA/g.
To sum up, the sodium-ion battery positive material A for preparing of the present invention and sodium-ion battery positive material B all has higher charge/discharge capacity, preferably high rate performance and cyclical stability.
Claims (10)
1. a sodium-ion battery positive material A, is characterized in that, described sodium-ion battery positive material A consists of Na (Na
xfe
1-x-y-zni
ymn
z) O
2, wherein 0<x≤0.2,0<y<0.4,0<z<0.4.
2. sodium-ion battery positive material A as claimed in claim 1, it is characterized in that, described x is 0.05≤x≤0.2, is preferably 0.05≤x≤0.1, is more preferably 0.05,0.1 or 0.2;
And/or described y is 0.1,0.2,0.25 or 0.3;
And/or described z is 0.1,0.2 or 0.3;
And/or described sodium-ion battery positive material A consists of Na (Na
0.1fe
0.5ni
0.2mn
0.2) O
2, Na (Na
0.05fe
0.4ni
0.25mn
0.3) O
2, Na (Na
0.1fe
0.3ni
0.3mn
0.3) O
2or Na (Na
0.2fe
0.6ni
0.1mn
0.1) O
2.
3. a sodium-ion battery positive material B, is characterized in that, described sodium-ion battery positive material B is the Surface coating one deck aluminium oxide at sodium-ion battery positive material A as claimed in claim 1 or 2;
Wherein, the covering amount of described aluminium oxide is preferably 0.5-2%, and described percentage is the mass percent of alumina phase for sodium-ion battery positive material B.
4. a preparation method of sodium-ion battery positive material A as claimed in claim 1 or 2, is characterized in that, it comprises the steps: presoma and sodium salt mixing, sintering, and cooling, obtains sodium-ion battery positive material A;
Wherein, described presoma is the solid obtained by the mixed aqueous solution of nickel salt, molysite and manganese salt, precipitation reagent and complexing agent hybrid reaction; The molar ratio of nickle atom, iron atom and manganese atom is y:(1-x-y-z): z, mole total amount sum of nickle atom, iron atom and manganese atom and the molar ratio of sodium atom are (1-x): (1+x), 0<x≤0.2,0<y<0.4,0<z<0.4.
5. preparation method as claimed in claim 4, it is characterized in that, the water in described mixed aqueous solution is deionized water;
And/or, described nickel salt be selected from nickelous sulfate, nickel chloride and nickel nitrate one or more;
And/or described molysite is selected from ferrous sulfate and/or frerrous chloride;
And/or, described manganese salt be selected from manganese sulfate, manganese chloride and manganese nitrate one or more;
And/or the concentration of described mixed aqueous solution is 1-2mol/L;
And/or described precipitation reagent is the aqueous solution of NaOH;
And/or the concentration of described precipitation reagent is 1-5mol/L;
And/or described complexing agent is the aqueous solution of ammoniacal liquor;
And/or the concentration of described complexing agent is 1-5mol/L.
6. preparation method as claimed in claim 4, is characterized in that, described presoma is by by described mixed aqueous solution, described precipitation reagent and described complexing agent and stream adds the solid carrying out hybrid reaction acquisition in reactor;
Wherein, the temperature of described reaction is preferably 40-60 DEG C; The time of described reaction is preferably 5-10 hour; The pH value of described reaction is preferably 9.0-11.5; The mixing speed of described reactor is preferably 400-800r/min; The flow that mixed aqueous solution adds reactor is preferably 6-200mL/min; The flow that precipitation reagent adds reactor is preferably 4-100mL/min; The flow that complexing agent adds reactor is preferably 4-100mL/min;
And/or, before presoma and sodium salt mixing, the reactant liquor by the mixed aqueous solution of nickel salt, molysite and manganese salt, precipitation reagent and complexing agent hybrid reaction is first carried out ageing, filters, washing, dry, obtain precursor powder;
Wherein, described ageing is preferably for leaving standstill 11-13 hour; Described washing preferably adopts deionized water to wash; The number of times of described washing is preferably twice; Described drying is preferably 95-103 DEG C dries 9-11 hour;
And/or, described sodium salt be selected from sodium carbonate, sodium nitrate and sodium acetate one or more;
And/or the atmosphere of described sintering is air atmosphere;
And/or the temperature of described sintering is 600-1000 DEG C;
And/or the time of described sintering is 10-20 hour;
And/or, described in be cooled to and naturally cool to room temperature.
7. a sodium-ion battery A, its positive pole comprises sodium-ion battery positive material A as claimed in claim 1 or 2.
8. the preparation method of a sodium-ion battery positive material B as claimed in claim 3, it is characterized in that, it comprises the steps: the Surface coating one deck aluminium oxide at sodium-ion battery positive material A as claimed in claim 1 or 2, obtains sodium-ion battery positive material B.
9. the preparation method of sodium-ion battery positive material B as claimed in claim 8, it is characterized in that, in described sodium-ion battery positive material B, the covering amount of aluminium oxide is 0.5-2%, and described percentage is the mass percent of alumina phase for sodium-ion battery positive material B;
And/or, carry out in the steps below in the operation of Surface coating one deck aluminium oxide of described sodium-ion battery positive material A: in water, by described sodium-ion battery positive material A and the mixing of aluminium salt, after the granulation of gained mixed liquor drying, heat treatment, obtains sodium-ion battery positive material B;
Wherein, described aluminium salt is preferably selected from aluminum nitrate and/or aluminum acetate; Described mixing preferably mixes in ultrasonic mode, and the described ultrasonic time is preferably 5-15 minute, and described ultrasonic temperature is preferably 20-30 DEG C; Preferably, adopt measuring pump to be transported to spray dryer described mixed liquor and carry out spray drying granulation; Described heat treatment is preferably heat-treated at granulation gained sample is placed in 300-450 DEG C, more preferably at granulation gained sample is placed in 300-450 DEG C, heat-treat 1-2 hour, best for the sample of granulation gained is placed in Muffle furnace, at 300-450 DEG C, heat-treat 1-2 hour; Preferably, carry out being cooled to room temperature after heat treatment, described cooling is preferably for naturally cooling;
Wherein, the charging rate of described measuring pump is preferably 2-10mL/min, and the inlet temperature of described spray dryer is preferably 200-250 DEG C, and the outlet temperature of described spray dryer is preferably 100-120 DEG C.
10. a sodium-ion battery B, its positive pole comprises sodium-ion battery positive material B as claimed in claim 3.
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