CN103050682A - Sodium ion battery electrode material and preparation method thereof - Google Patents
Sodium ion battery electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a sodium ion battery electrode material and a preparation method thereof and belongs to the technical field of sodium ion batteries. The composition of the electrode material is (yNaFe1/2Ni1/2O2-(1-y)Na2MnO3), wherein y is 0.1-0.5. The preparation method of the electrode material comprises the following steps: dissolving hydroxide easy to dissolve in water into the water to obtain hydroxide solution; dissolving soluble manganese salt, iron salt and nickel salt into water to obtain salt solution; mixing the hydroxide solution with the salt solution to obtain mixed liquid, agitating the mixed liquid for 10-30 hours, washing and filtering, and vacuum-drying to obtain a precursor; and uniformly mixing the precursor with sodium salt and calcining for more than or equal to 10 hours at a temperature of 500-1,000 DEG C to obtain the electrode material. The electrode material has the advantages of better cycling performance, higher coulombic efficiency, greenness and environmental friendliness, and low cost; and the trivalent iron salt is taken as a raw material in the preparation method, so that the preparation method is simple and convenient.
Description
Technical field
The present invention relates to a kind of sodium-ion battery electrode material and preparation method thereof, wherein, specifically, described electrode material consist of (yNaFe
1/2Ni
1/2O
2-(1-y) Na
2MnO
3), can be used as the positive electrode of sodium-ion battery, belong to the sodium-ion battery technical field.
Background technology
Along with the environmental problem that continuous minimizing and the use thereof of non-renewable fossil energy brings, the conversion of the regenerative resource of cleaning and store and become gradually the focus that people pay close attention to.Force people to go to develop and seek clean regenerative resource, such as: wind energy, solar energy and tidal energy etc., and the noncontinuity of described regenerative resource energy and instability can't normally be connected to the grid it, can only temporarily store by energy storage device, utilize afterwards again.In existing secondary cell, lithium ion battery is because the advantages such as its high-energy-density and high voltage become the optimal electrical source of power of pure electric vehicle and hybrid vehicle; In portable type electronic product market, lithium ion battery is come out top especially.But the maximum problem of at present lithium ion battery existence is exactly the high production cost of lithium and the deficiency of resource.The gross reserves of lithium carbonate is 4,000 ten thousand tons in Global land and the salt lake, and this enough produces the required lithium ion battery of electric motor car of about 1,000,000,000 40kWh, but the Global Auto recoverable amount is above 1,000,000,000 now, and the automobile zero discharge trend that is inevitable, so lithium can only be recycling, so just further improved the production cost of lithium ion battery.Along with the continuous increase of Global Auto recoverable amount, it is more obvious that the deficiency of lithium resource just seems.Although a large amount of lithiums is arranged in the seawater, leaching process very complex and cost are very high.
The problem that sodium-ion battery mainly exists is that cycle performance is relatively poor, and irreversible capacity loss is larger; Enclosed pasture efficient is lower.But aspect extensive energy storage, the researcher extremely favors sodium-ion battery because it have raw material wide material sources, cost low, can adopt the lower characteristics such as electrolyte of decomposition voltage, reduced production cost, improved the fail safe of sodium-ion battery.Over a long time and for the large-scale energy storage device, it is not very high that the weight and volume of sodium-ion battery requires, so sodium-ion battery is only selection for regenerative resource; And the working mechanism of sodium-ion battery is similar with lithium ion battery.Although the research about it is just at the early-stage, sodium-ion battery begins to be paid close attention to by the countries in the world researcher gradually and become study hotspot, believes that high performance sodium-ion battery can be widely used in the near future.
The positive electrode of sodium-ion battery is the key point of sodium-ion battery performance.At present, in the sodium-ion battery positive electrode that document is reported, oxide material mainly contains Na
xCoO
2And Na
xMnO
2, Na
xCoO
2The a plurality of discharge platforms of appearance and cycle performance are bad in discharge process.The traditional solid phase method of the usefulness such as Tarascon is synthetic and studied Na
0.44MnO
2The performance of/C battery during as positive pole; High rate performance and the capability retention of this material are bad, after 50 weeks of C/10 circulation capacity attenuations half.The electrode material granules that traditional high temperature solid-state method obtains is large, is unfavorable for that its chemical property improves; The electrode material of sol-gel synthesis is easily reunited, and density is low, does not have large breakthrough for improving its chemical property; And chemical coprecipitation directly obtains chemical composition homogeneous and the little Powder electrode material of granularity by the various chemical reactions in the solution.
Summary of the invention
Relatively poor for sodium-ion battery cycle performance in the prior art, enclosed pasture efficient lower defective, one of purpose of the present invention is to provide a kind of sodium-ion battery electrode material, wherein, described electrode material consist of (yNaFe
1/2Ni
1/2O
2-(1-y) Na
2MnO
3), described electrode material can be used as the positive electrode of sodium-ion battery, and described electrode material has good cycle performance and higher enclosed pasture efficient.
Two of purpose of the present invention is to provide a kind of preparation method of sodium-ion battery electrode material, of the present invention a kind of sodium-ion battery electrode material that described method adopts chemical coprecipitation and high-temperature calcination two-step method to prepare.
For realizing purpose of the present invention, provide following technical scheme.
A kind of sodium-ion battery electrode material, described electrode material consist of (yNaFe
1/2Ni
1/2O
2-(1-y) Na
2MnO
3), wherein, y is 0.1～0.5.
A kind of preparation method of sodium-ion battery electrode material of the present invention, described method step is as follows:
One, liquid phase reactor
(1) will be easy to become solution in the water-soluble hydroxide solution that obtains of hydroxide of water;
Described hydroxide can be a kind of in lithium hydroxide, NaOH or the potassium hydroxide;
(2) with manganese salt, molysite and the nickel salt of the solubility salting liquid that obtains soluble in water;
Described manganese salt is preferably a kind of in manganese chloride, manganese sulfate or the manganese nitrate, and molysite is preferably a kind of in iron chloride, ferric nitrate or the ferric sulfate, and nickel salt is preferably a kind of in nickel chloride, nickel nitrate or the nickelous sulfate;
(3) hydroxide solution and salt solution mix are obtained mixed liquor, behind mixed liquor stirring 10～30h, washing also filters to remove excessive hydroxide solution excessively, and vacuumize obtains presoma;
Can be at 60～100 ℃ of lower vacuumize 6～48h;
Water described in step (1)～(3) is the water of purity 〉=deionized water purity;
Step 2, high temperature solid-phase sintering
Described presoma and sodium salt are mixed, at 500～1000 ℃ of lower calcining 〉=10h, obtain a kind of sodium-ion battery electrode material of the present invention;
Described sodium salt is preferably a kind of in NaOH, sodium carbonate, sodium oxalate, sodium acetate or the natrium citricum;
Mixed method can be mechanical ball milling mix or adopt presoma and sodium salt mixed in the volatile organic solvent after, organic solvent is volatilized fully, then calcining; Preferred calcining 10～24h.
A kind of sodium-ion battery, the positive electrode of described battery are a kind of sodium-ion battery electrode material of the present invention.
Beneficial effect
1. the invention provides a kind of sodium-ion battery electrode material, described electrode material has cycle performance better and the higher characteristics of enclosed pasture efficient, is a kind of novel energy-storing sodium ion positive electrode of environmental protection;
2. the invention provides a kind of sodium-ion battery electrode material, described materials'use is at distributed more widely, the cheap and eco-friendly raw material of occurring in nature, greatly reduces cost of material and to the pollution of environment;
3. the invention provides a kind of sodium-ion battery electrode material, described electrode material is during as sodium-ion battery anodal, and after several weeks, discharge capacity can improve in initial cycle;
4. the invention provides a kind of preparation method of sodium-ion battery electrode material, use trivalent iron salt as raw material, so that described method is simple and convenient in the described method.
Description of drawings
Fig. 1 is the X-ray diffractogram of the sodium-ion battery electrode material that makes of embodiment 1.
Fig. 2 is the X-ray diffractogram of the sodium-ion battery electrode material that makes of embodiment 2.
Fig. 3 is the X-ray diffractogram of the sodium-ion battery electrode material that makes of embodiment 3.
Fig. 4 is the X-ray diffractogram of the sodium-ion battery electrode material that makes of embodiment 4.
Fig. 5 is the X-ray diffractogram of the sodium-ion battery electrode material that makes of embodiment 5.
Fig. 6 is the X-ray diffractogram of the sodium-ion battery electrode material that makes of embodiment 6.
Fig. 7 is the scanning electron microscope (SEM) photograph of the sodium-ion battery electrode material that makes of embodiment 1.
Embodiment
For better understanding the present invention, below in conjunction with specific embodiment the present invention is done to describe in further detail.
Embodiment 1
Take by weighing 2.0g potassium hydroxide (KOH) and add in the 70ml deionized water, stir and make its dissolving, obtain potassium hydroxide solution; Take by weighing 3.56g tetrahydrate manganese chloride, 0.40g nine water ferric nitrates and 0.29g six water nickel nitrates and be dissolved in the 70ml deionized water, stir and make its dissolving, obtain salting liquid; Potassium hydroxide solution and salt solution mix are obtained mixed liquor, with mixed liquor stirring at normal temperature 20h, then wash 8 times, filtration, obtain the co-precipitation of presoma hydroxide at 90 ℃ of lower vacuumize 15h; Then in the 30ml medium-acetone, be the planetary ball mill of 400r/min on mechanical ball milling 1h after at rotating speed with presoma and 2.55g sodium oxalate, under 70 ℃, acetone is volatilized fully, obtain mixture, mixture is calcined 20h in Muffle furnace, obtain a kind of sodium-ion battery electrode material (yNaFe of the present invention under 850 ℃
1/2Ni
1/2O
2-(1-y) Na
2MnO
3), wherein, y is 0.1.
Fig. 1 is the X-ray diffractogram of the sodium-ion battery electrode material that makes of embodiment 1, wherein ordinate is X ray intensity, abscissa is the X-ray scanning angle, described electrode material locates to have characteristic peak on (002) crystal face 15.84 ° of scanning angles, locate to have characteristic peak on (110) crystal face 19.96 ° of scanning angles, locate to have characteristic peak on (004) crystal face 32.02 ° of scanning angles, locate to have characteristic peak on (111) crystal face 32.94 ° of scanning angles, locate to have characteristic peak on (100) crystal face 35.78 ° of scanning angles, locate to have characteristic peak on (102) crystal face 39.36 ° of scanning angles, locate to have characteristic peak on (103) crystal face 43.46 ° of scanning angles, locate to have characteristic peak on (104) crystal face 48.76 ° of scanning angles, locate to have characteristic peak on (106) crystal face 62 ° of scanning angles, locate to have characteristic peak on (110) crystal face 64.26 ° of scanning angles, locate to have characteristic peak on (008) crystal face 66.7 ° of scanning angles, in X-ray diffractogram, without assorted peak, illustrate that described electrode material is the pure phase material.
Embodiment 2
Take by weighing 2.0g potassium hydroxide and add in the 60ml deionized water, stir and make its dissolving, obtain potassium hydroxide solution; Take by weighing 3.17g tetrahydrate manganese chloride, 0.81g nine water ferric nitrates and 0.58g six water nickel nitrates and be dissolved in the 70ml deionized water, stir and make its dissolving, obtain salting liquid; Potassium hydroxide solution and salt solution mix are obtained mixed liquor, with mixed liquor stirring at normal temperature 20h, then wash 8 times, filtration, obtain the co-precipitation of presoma hydroxide at 70 ℃ of lower vacuumize 30h; Then in the 30ml medium-acetone, be the planetary ball mill of 400r/min on mechanical ball milling 2h after at rotating speed with presoma and 2.41g sodium oxalate, under 70 ℃, acetone is volatilized fully, obtain mixture, mixture is calcined 20h in Muffle furnace, obtain a kind of sodium-ion battery electrode material (yNaFe of the present invention under 900 ℃
1/2Ni
1/2O
2-(1-y) Na
2MnO
3), wherein, y is 0.2.
Fig. 2 is the X-ray diffractogram of the sodium-ion battery electrode material that makes of embodiment 2, wherein ordinate is X ray intensity, abscissa is the X-ray scanning angle, described positive electrode locates to have characteristic peak on (002) crystal face 15.84 ° of scanning angles, locate to have characteristic peak on (110) crystal face 19.96 ° of scanning angles, locate to have characteristic peak on (004) crystal face 32.02 ° of scanning angles, locate to have characteristic peak on (111) crystal face 32.94 ° of scanning angles, locate to have characteristic peak on (100) crystal face 35.78 ° of scanning angles, locate to have characteristic peak on (102) crystal face 39.36 ° of scanning angles, locate to have characteristic peak on (103) crystal face 43.46 ° of scanning angles, locate to have characteristic peak on (104) crystal face 48.76 ° of scanning angles, locate to have characteristic peak on (106) crystal face 62 ° of scanning angles, locate to have characteristic peak on (110) crystal face 64.26 ° of scanning angles, locate to have characteristic peak on (008) crystal face 66.7 ° of scanning angles, in X-ray diffractogram, without assorted peak, illustrate that described electrode material is the pure phase material.
Embodiment 3
Take by weighing 2.0g potassium hydroxide and add in the 60ml deionized water, stir and make its dissolving, obtain potassium hydroxide solution; Take by weighing 2.77g tetrahydrate manganese chloride, 1.21g nine water ferric nitrates and 0.87g six water nickel nitrates and be dissolved in the 70ml deionized water, stir and make its dissolving, obtain salting liquid; Potassium hydroxide solution and salt solution mix are obtained mixed liquor, with mixed liquor stirring at normal temperature 20h, then wash 8 times, filtration, obtain the co-precipitation of presoma hydroxide at 100 ℃ of lower vacuumize 8h; Then in the 30ml medium-acetone, be the planetary ball mill of 400r/min on mechanical ball milling 1h after at rotating speed with presoma and 2.79g sodium acetate, under 70 ℃, acetone is volatilized fully, obtain mixture, mixture is calcined 20h in Muffle furnace, obtain a kind of sodium-ion battery electrode material (yNaFe of the present invention under 850 ℃
1/2Ni
1/2O
2-(1-y) Na
2MnO
3), wherein, y is 0.3.
Fig. 3 is the X-ray diffractogram of the sodium-ion battery electrode material that makes of embodiment 3, wherein ordinate is X ray intensity, abscissa is the X-ray scanning angle, described electrode material locates to have characteristic peak on (002) crystal face 15.96 ° of scanning angles, locate to have characteristic peak on (110) crystal face 20.26 ° of scanning angles, locate to have characteristic peak on (004) crystal face 32.2 ° of scanning angles, locate to have characteristic peak on (006) crystal face 32.98 ° of scanning angles, locate to have characteristic peak on (101) crystal face 35.6 ° of scanning angles, locate to have characteristic peak on (112) crystal face 39.26 ° of scanning angles, locate to have characteristic peak on (023) crystal face 41.7 ° of scanning angles, locate to have characteristic peak on (113) crystal face 43.42 ° of scanning angles, locate to have characteristic peak on (114) crystal face 48.8 ° of scanning angles, locate to have characteristic peak on (106) crystal face 62.22 ° of scanning angles, locate to have characteristic peak on (110) crystal face 64 ° of scanning angles, locate to have characteristic peak on (008) crystal face 66.44 ° of scanning angles, in X-ray diffractogram, without assorted peak, illustrate that described electrode material is the pure phase material.
Embodiment 4
Take by weighing 1.9g Lithium hydroxide monohydrate (LiOHH
2O) add in the 50ml water, stir and make its dissolving, obtain lithium hydroxide solution; Take by weighing 2.37g tetrahydrate manganese chloride, 1.62g nine water ferric nitrates and 1.16g six water nickel nitrates and be dissolved in the 70ml water, stir and make its dissolving, obtain salting liquid; Lithium hydroxide solution and salt solution mix are obtained mixed liquor, with mixed liquor stirring at normal temperature 20h, then wash 6 times, filtration, obtain the co-precipitation of presoma hydroxide at 90 ℃ of lower vacuumize 6h; Then with presoma and 2.14g sodium oxalate in the 30ml absolute ethyl alcohol behind ultrasonic concussion 1h, under 75 ℃, absolute ethyl alcohol is volatilized fully, obtain mixture, mixture is calcined 10h in Muffle furnace under 1000 ℃, obtain a kind of sodium-ion battery electrode material (yNaFe of the present invention
1/2Ni
1/2O
2-(1-y) Na
2MnO
3), wherein, y is 0.4.
Fig. 4 is the X-ray diffractogram of the sodium-ion battery electrode material that makes of embodiment 4, wherein ordinate is X ray intensity, abscissa is the X-ray scanning angle, described electrode material locates to have characteristic peak on (003) crystal face 16.42 ° of scanning angles, locate to have characteristic peak on (111) crystal face 21.28 ° of scanning angles, locate to have characteristic peak on (006) crystal face 33.2 ° of scanning angles, locate to have characteristic peak on (101) crystal face 35.56 ° of scanning angles, locate to have characteristic peak on (012) crystal face 36.9 ° of scanning angles, locate to have characteristic peak on (104) crystal face 41.82 ° of scanning angles, locate to have characteristic peak on (107) crystal face 53.42 ° of scanning angles, locate to have characteristic peak on (013) crystal face 58.16 ° of scanning angles, locate to have characteristic peak on (110) crystal face 63.04 ° of scanning angles, locate to have characteristic peak on (113) crystal face 65.62 ° of scanning angles, in X-ray diffractogram, without assorted peak, illustrate that described electrode material is the pure phase material.
Embodiment 5
Take by weighing 2.00g NaOH (NaOH) and add in the 70ml deionized water, stir and make its dissolving, obtain sodium hydroxide solution; Take by weighing 2.37g tetrahydrate manganese chloride, 1.62g nine water ferric nitrates and 1.16g six water nickel nitrates and be dissolved in the 70ml deionized water, stir and make its dissolving, obtain salting liquid; Sodium hydroxide solution and salt solution mix are obtained mixed liquor, with mixed liquor stirring at normal temperature 20h, then wash 5 times, filtration, obtain the co-precipitation of presoma hydroxide at 60 ℃ of lower vacuumize 48h; Then after presoma and 1.70g sodium carbonate being stirred 1h in the 30ml absolute ethyl alcohol, under 75 ℃, absolute ethyl alcohol is volatilized fully, obtain mixture, mixture is calcined 18h in Muffle furnace under 700 ℃, obtain a kind of sodium-ion battery electrode material (yNaFe of the present invention
1/2Ni
1/2O
2-(1-y) Na
2MnO
3), wherein, y is 0.4.
Fig. 5 is the X-ray diffractogram of the sodium-ion battery electrode material that makes of embodiment 5, wherein ordinate is X ray intensity, abscissa is the X-ray scanning angle, described electrode material locates to have characteristic peak on (003) crystal face 16.42 ° of scanning angles, locate to have characteristic peak on (111) crystal face 21.28 ° of scanning angles, locate to have characteristic peak on (006) crystal face 33.2 ° of scanning angles, locate to have characteristic peak on (101) crystal face 35.56 ° of scanning angles, locate to have characteristic peak on (012) crystal face 36.9 ° of scanning angles, locate to have characteristic peak on (104) crystal face 41.82 ° of scanning angles, locate to have characteristic peak on (107) crystal face 53.42 ° of scanning angles, locate to have characteristic peak on (013) crystal face 58.16 ° of scanning angles, locate to have characteristic peak on (110) crystal face 63.04 ° of scanning angles, locate to have characteristic peak on (113) crystal face 65.62 ° of scanning angles, in X-ray diffractogram, without assorted peak, illustrate that described electrode material is the pure phase material.
Embodiment 6
Take by weighing 2.6g potassium hydroxide and add in the 70ml deionized water, stir and make its dissolving, obtain potassium hydroxide solution; Take by weighing 1.98g tetrahydrate manganese chloride, 2.02g nine water ferric nitrates and 1.45g six water nickel nitrates and be dissolved in the 70ml water, stir and make its dissolving, obtain salting liquid; Potassium hydroxide solution and salt solution mix are obtained mixed liquor, with mixed liquor stirring at normal temperature 10h, then wash 7 times, filtration, obtain the co-precipitation of presoma hydroxide at 80 ℃ of lower vacuumize 8h; Then after presoma and 1.20g NaOH being stirred 1h in the 30ml absolute ethyl alcohol, under 75 ℃, absolute ethyl alcohol is volatilized fully, obtain mixture, mixture is calcined 12h in Muffle furnace under 500 ℃, obtain a kind of sodium-ion battery electrode material (yNaFe of the present invention
1/2Ni
1/2O
2-(1-y) Na
2MnO
3), wherein, y is 0.5.
Fig. 6 is the X-ray diffractogram of the sodium-ion battery electrode material that makes of embodiment 6, wherein ordinate is X ray intensity, abscissa is the X-ray scanning angle, described positive electrode locates to have characteristic peak on (003) crystal face 16.62 ° of scanning angles, locate to have characteristic peak on (006) crystal face 33.42 ° of scanning angles, locate to have characteristic peak on (101) crystal face 35.56 ° of scanning angles, locate to have characteristic peak on (012) crystal face 36.94 ° of scanning angles, locate to have characteristic peak on (104) crystal face 41.84 ° of scanning angles, locate to have characteristic peak on (107) crystal face 53.58 ° of scanning angles, locate to have characteristic peak on (013) crystal face 58.32 ° of scanning angles, locate to have characteristic peak on (110) crystal face 62.9 ° of scanning angles, locate to have characteristic peak on (113) crystal face 65.42 ° of scanning angles, in X-ray diffractogram, without assorted peak, illustrate that described electrode material is the pure phase material.
In above-described embodiment 1～6, adopt the Rigaku-D/max-2550pc type x-ray powder diffraction instrument of HIT that the sodium-ion battery electrode material that embodiment 1～6 makes is carried out material phase analysis, obtain respectively X-ray diffractogram, shown in Fig. 1～6.Adopt the sem test instrument of the S-4800 model of HITACHI company production, accelerating voltage is 20KV, the pattern of the sodium-ion battery electrode material that observation embodiment 1～6 makes, find that the granularity of described battery material is little and be evenly distributed that the scanning electron microscope (SEM) photograph of the sodium-ion battery electrode material that embodiment 1 makes as shown in Figure 7.
The sodium-ion battery electrode material that embodiment 1～6 is made is assembled into respectively in 6 button cells, and described button cell preparation method is as follows:
With described sodium-ion battery electrode material as positive electrode active materials, positive electrode active materials, binding agent Kynoar (PVDF), acetylene black are mixed with the ratio of mass ratio 8:1:1, be uniformly coated into thin layer at aluminium foil, be cut into disk after the drying as positive electrode, the sodium metal sheet is as negative pole, Celgard 2300 is barrier film, 1.0mol/L NaClO
4/ EC(ethylene carbonate)+and the DMC(dimethyl carbonate) (volume ratio of EC and DMC is 1:1) be electrolyte, is assembled into the CR2025 button cell in the argon gas glove box.
With the Land cell tester that the Jin Nuo of Wuhan City Electronics Co., Ltd. produces described button cell is tested, test condition and result are as follows:
Button cell is at 20mA g
-1Current density under constant current charge-discharge, the charging/discharging voltage interval is 1.5～4.0V, the enclosed pasture efficient of each circulation is more than 96%, the specific discharge capacity after circulating for 50 times is maintained at about 88% of initial discharge capacity.
The present invention includes but be not limited to above embodiment, every any being equal to of carrying out under the spirit and principles in the present invention, replace or local improvement, all will be considered as within protection scope of the present invention.
Claims (11)
1. sodium-ion battery electrode material is characterized in that: described electrode material consist of (yNaFe
1/2Ni
1/2O
2-(1-y) Na
2MnO
3), y is 0.1～0.5.
2. the preparation method of a sodium-ion battery electrode material as claimed in claim 1, it is characterized in that: step is as follows:
(1) will be easy to become solution in the water-soluble hydroxide solution that obtains of hydroxide of water;
(2) with the water-soluble salting liquid that obtains of soluble manganese salt, molysite and nickel salt;
(3) hydroxide solution and salt solution mix are obtained mixed liquor, behind mixed liquor stirring 10～30h, washing is also filtered, and vacuumize obtains presoma;
(4) presoma and sodium salt are mixed, at 500～1000 ℃ of lower calcining 〉=10h, obtain a kind of sodium-ion battery electrode material;
Wherein, water described in step (1)～(3) is the water of purity 〉=deionized water purity.
3. the preparation method of a kind of sodium-ion battery electrode material according to claim 2 is characterized in that: hydroxide is lithium hydroxide, NaOH or potassium hydroxide in the step (1).
4. the preparation method of a kind of sodium-ion battery electrode material according to claim 2 is characterized in that: manganese salt is manganese chloride, manganese sulfate or manganese nitrate in the step (2).
5. the preparation method of a kind of sodium-ion battery electrode material according to claim 2 is characterized in that: molysite is iron chloride, ferric nitrate or ferric sulfate in the step (2).
6. the preparation method of a kind of sodium-ion battery electrode material according to claim 2 is characterized in that: nickel salt is nickel chloride, nickel nitrate or nickelous sulfate in the step (2).
7. the preparation method of a kind of sodium-ion battery electrode material according to claim 2 is characterized in that: in the step (3) at 60～100 ℃ of lower vacuumize 6～48h.
8. the preparation method of a kind of sodium-ion battery electrode material according to claim 2 is characterized in that: sodium salt is NaOH, sodium carbonate, sodium oxalate, sodium acetate or natrium citricum in the step (4).
9. the preparation method of a kind of sodium-ion battery electrode material according to claim 2, it is characterized in that: in the step (4) mechanical ball milling mix or adopt presoma and sodium salt mixed in the volatile organic solvent after, organic solvent is volatilized fully, then calcining.
10. the preparation method of a kind of sodium-ion battery electrode material according to claim 8 is characterized in that: calcining 10～24h in the step (4).
11. a sodium-ion battery is characterized in that: the positive electrode of described battery is a kind of sodium-ion battery electrode material as claimed in claim 1.
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| CN103311538A (en) * | 2013-05-06 | 2013-09-18 | 北京理工大学 | Binary positive material of sodium ion batteries and preparation method thereof |
| CN103474659A (en) * | 2013-08-23 | 2013-12-25 | 中国科学院化学研究所 | Preparation method and application of positive pole material of sodium-ion battery |
| CN103531778A (en) * | 2013-10-28 | 2014-01-22 | 北京理工大学 | Solid solution sodium-ion battery positive material and preparation method therefor |
| CN103594707A (en) * | 2013-11-29 | 2014-02-19 | 西南大学 | High-temperature solid-phase synthesis method of one-dimensional nano-sodion cell anode material NaxMnO2 |
| CN104009230A (en) * | 2014-05-30 | 2014-08-27 | 深圳市巨兆数码有限公司 | Lithium ion battery anode material and lithium ion battery |
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| CN105692721A (en) * | 2016-01-29 | 2016-06-22 | 太原理工大学 | Sodium ion battery positive electrode material, and preparation method and application method thereof |
| CN109830671A (en) * | 2019-03-06 | 2019-05-31 | 四川大学 | A kind of tunnel recombination structure material and the sodium-ion battery positive material using tunnel recombination structure material preparation |
| CN113937286A (en) * | 2020-06-29 | 2022-01-14 | 溧阳中科海钠科技有限责任公司 | Coating modified sodium ion battery positive electrode material, preparation method thereof and battery |
| WO2024087568A1 (en) * | 2022-10-25 | 2024-05-02 | 湖北亿纬动力有限公司 | Manganese-based solid solution positive electrode material, preparation method therefor and use thereof |
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| CN113937286A (en) * | 2020-06-29 | 2022-01-14 | 溧阳中科海钠科技有限责任公司 | Coating modified sodium ion battery positive electrode material, preparation method thereof and battery |
| CN113937286B (en) * | 2020-06-29 | 2023-08-29 | 溧阳中科海钠科技有限责任公司 | Coated modified sodium ion battery positive electrode material, preparation method thereof and battery |
| WO2024087568A1 (en) * | 2022-10-25 | 2024-05-02 | 湖北亿纬动力有限公司 | Manganese-based solid solution positive electrode material, preparation method therefor and use thereof |
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