CN105552347B - A kind of anode material of lithium-ion battery and preparation method thereof, sodium-ion battery - Google Patents
A kind of anode material of lithium-ion battery and preparation method thereof, sodium-ion battery Download PDFInfo
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- CN105552347B CN105552347B CN201610130461.XA CN201610130461A CN105552347B CN 105552347 B CN105552347 B CN 105552347B CN 201610130461 A CN201610130461 A CN 201610130461A CN 105552347 B CN105552347 B CN 105552347B
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of anode material of lithium-ion battery and preparation method thereof, sodium-ion battery.It comprises the following steps：Under reducing atmosphere, after presoma is sintered, cooling, produce；Presoma is the solid by by the mixed liquor containing graphene, titanium dioxide, pink salt and mantoquita, being obtained with precipitant mix reaction；The mol ratio of tin element, copper and titanium elements is x：(1‑x)：1,0<x≤0.5.The preparation method of the present invention is easy, obtained material, is mutually cooperateed between each raw material components, not only effectively reduces the reuniting effect of tin copper particle, it is suppressed that tin forms the bulk effect of alloy with sodium in discharge process；And cycle performance, stability, electrical conductivity and the charge/discharge capacity of material can be taken into account；The anode material of lithium-ion battery of the present invention can be applied to prepare Soft Roll sodium-ion battery, and sodium-ion battery compares for lithium ion battery, green, safe, cheap, have very big advantage as stored energy application.
Description
Technical field
The present invention relates to a kind of sodium ion negative material and preparation method thereof, sodium-ion battery.
Background technology
Energy storage technology is one of important way that the regenerative resources such as wind energy, solar energy efficiently utilize, and power network Pinggu
The important means of peak regulation.In existing scale energy storage mode, electrochemical energy storage system with its it is efficient, flexible the characteristics of by wide
General concern, and domestic and international study hotspot at present, secondary cell, particularly lithium ion battery are placed high hopes by people in recent years.
However, for lithium ion battery energy storage system, as the key element lithium for supporting its development, maldistribution of the resources, reserves are limited,
Cost is higher to turn into an important factor for restricting its extensive stored energy application.Compare lithium resource, sodium element in earth reserves very
Abundant, widely distributed, refinement simply, considers that sodium-ion battery has cost degradation advantage, is expected to from resource and environment etc.
Realize extensive stored energy application.
Sodium-ion battery has the advantage in the majority such as cheap, green, but there is also challenge simultaneously.Sodium ion radius
Greatly, alternative positive and negative pole material system is very limited, particularly the missing of the negative material of excellent performance, seriously restricts sodium
The practical progress of ion battery.Result of study shows transition metal simple substance and its composite with preferably reversible embedding/de-
Sodium characteristic, as tin and sodium form Na15Sn4When, there is 847mAhg-1Theoretical capacity.Transition metal-type material is as sodium ion
GND has a clear superiority, but its challenge is also very big, with Sn or its alloy carry out it is embedding/de- during volumetric expansion receive
Contracting effect is obvious, and repeated charge rear electrode material easily ruptures, and causes battery capacity decay, cycle performance to be deteriorated.
Huang et al. (Nano Lett., 2012,12:5897-5902) first passage in situ TEM observes Sn electrodes in embedding sodium
During Volume Changes process：Volume Changes are about 420%.Mechanical stress caused by so big bulk effect can make electricity
Pole active material crushes, and the electrical contact with collector is lost, so as to cause the decay of electrode electro Chemical cycle performance.Xiao et al.
(Chem.Commun.,2012,48:3321) a nanometer Sn/C compounds are prepared for using solid-phase ball milling method, the reversible storage sodium of first circle holds
Measure as 544mAhg-1, but capability retention only has 79%, and material prepared by solid-phase ball milling method after 50 cycle periods
Particle size is uneven, reunites between particle serious, and the chemical property for restricting material plays, as the discharge capacity of material is low,
Cyclical stability difference and high rate performance difference etc..Therefore, suitable material structure is designed to suppress the volume of tin base cathode material
Effect, and the specific capacity for taking into account material just turns into one of focus direction in the research of current sodium-ion battery.
The content of the invention
The technical problems to be solved by the invention be to overcome sodium-ion battery tin base cathode material in the prior art it is embedding/
Volumetric expansion blockage effect is obvious in de- process, and repeated charge rear electrode material easily ruptures, and causes battery capacity
Decay, cycle performance decay, stability are undesirable and the defects of can not take into account material specific capacity, there is provided a kind of sodium ion
Cell negative electrode material and preparation method thereof, sodium-ion battery.The preparation method of the present invention is easy, obtained sodium ion negative pole material
Expect, mutually acted synergistically between each raw material components, not only effectively reduce tin copper particle (50~200nm of grain size) group
Poly- effect, it is suppressed that tin forms the bulk effect of alloy with sodium in discharge process；And the cycle performance, steady of material can be taken into account
Qualitative, electrical conductivity and charge/discharge capacity, greatly improve its chemical property.Especially high rate performance and cycle performance,
In a certain embodiment, when current density is 200mA/g, the 1C discharge capacities of obtained sodium ion negative material reach 408mAh/
G, after 50 cycle periods, battery capacity conservation rate 93%.The anode material of lithium-ion battery of the present invention can be applied to prepare soft
Bag sodium-ion battery, sodium-ion battery compare for lithium ion battery, green, safe, cheap, have very as stored energy application
Big advantage.
The present invention solves above-mentioned technical problem by the following technical programs.
The invention provides a kind of preparation method of anode material of lithium-ion battery, it comprises the following steps：In reproducibility
Under atmosphere, after presoma is sintered, cooling, anode material of lithium-ion battery is produced；
Wherein, the presoma is by by the mixed liquor containing graphene, titanium dioxide, pink salt and mantoquita, with precipitation
The solid that agent hybrid reaction obtains；The mol ratio of tin element, copper and titanium elements is x：(1-x)：1,0<x≤0.5.
In the present invention, the reducing atmosphere is that chemical field is conventional, is generally referred in the environment containing reducibility gas
Under.The reducibility gas is that chemical field is conventional, generally comprises hydrogen and/or carbon monoxide, preferably hydrogen.The reduction
Property atmosphere be preferably hydrogen and argon gas composition mixed atmosphere, more preferably hydrogen and argon gas is with 5：95 volume ratio composition mixes
Close atmosphere.
In the present invention, the x preferably 0.1≤x≤0.5, more preferably 0.3≤x≤0.5, most preferably 0.4.
In the present invention, the graphene is that this area is conventional, preferably 1~10 layer of graphene, more preferably mono-layer graphite
Alkene or 5~10 layers of graphene.
In the present invention, the dosage of the graphene is conventional for this area, preferably 2~10%, more preferably 8%, above-mentioned percentage
Than being graphene quality relative to tin element and the mass percent of copper gross mass.
In the present invention, the particle diameter of the titanium dioxide is conventional for this area, preferably 50~400nm, more preferably 180~
220nm, most preferably 200nm.
In the present invention, the pink salt is the conventional use of pink salt in sodium-ion battery field, preferably include butter of tin and/or
Stannous chloride, more preferably butter of tin.
In the present invention, the mantoquita is the conventional mantoquita of chemical field, preferably includes copper sulphate and/or copper chloride, more excellent
Select copper sulphate.
In the present invention, the preferred deionized water of solvent in the mixed liquor.
In the present invention, in the mixed liquor, the total concentration of pink salt and mantoquita is in the art conventional, preferably 1~2mol/L.
In the present invention, the precipitating reagent is anode material of lithium-ion battery field routine precipitating reagent, preferably sodium hydroxide
The aqueous solution.The concentration of the precipitating reagent is in the art conventional, preferably 1~5mol/L, more preferably 3mol/L.
In the present invention, the presoma is added in the reactor containing the mixed liquor preferably through by the precipitating reagent
Carry out the solid of hybrid reaction acquisition.
Wherein, the temperature of the reaction is that this area is conventional, preferably 40~60 DEG C, more preferably 50 DEG C.The reaction when
Between for this area it is conventional, preferably 1~5 hour, more preferably 2 hours.The pH value of the reaction is that this area is conventional, preferably 9.0~
11.5, more preferably 10.5.The mixing speed of the reactor is in the art conventional, preferably 400~800r/min, more preferably
500r/min or 600r/min.The flow that the precipitating reagent adds reactor is this area regular flow, preferably 4~100mL/
Min, more preferably 40mL/min.
In the present invention, it is preferable that after the hybrid reaction, the reaction solution of the mixed liquor and the precipitating reagent is carried out old
Change, filter, wash, dry, obtain presoma solid.
Wherein, the ageing is routine operation in the art, preferably stands 11~13 hours, more preferably stands 12 hours.
It is described to be filtered into this area routine operation.The washing is this area routine operation, it is preferred to use deionized water is washed.Institute
It is conventional for this area to state the number of washing, preferably twice.The operation of the drying is this area routine operation, preferably 95~105
DEG C drying 9~11 hours, more preferably 100 DEG C dry 10 hours.
In the present invention, the temperature of the sintering is in the art conventional, preferably 400~700 DEG C, more preferably 500 DEG C or 600
℃.The time of the sintering is that this area is conventional, preferably 2~6 hours, more preferably 5 hours.
In the present invention, the operation of the cooling is conventional for this area, preferably naturally cools to room temperature.
Present invention also offers one kind anode material of lithium-ion battery as made from above-mentioned preparation method.
Present invention also offers a kind of sodium-ion battery, its negative pole includes the anode material of lithium-ion battery.
It on the basis of common sense in the field is met, above-mentioned each optimum condition, can be combined, it is each preferably real to produce the present invention
Example.
Agents useful for same and raw material of the present invention are commercially available.
The positive effect of the present invention is：
The preparation method of the present invention is easy, obtained sodium ion negative material, is mutually acted synergistically between each raw material components,
Not only effectively reduce tin copper particle (50~200nm of grain size) reuniting effect, it is suppressed that in discharge process tin with
Sodium forms the bulk effect of alloy；And cycle performance, stability, electrical conductivity and the charge/discharge capacity of material, pole can be taken into account
Big improves its chemical property.Especially high rate performance and cycle performance, in a certain embodiment, current density 200mA/
During g, the 1C discharge capacities of obtained sodium ion negative material reach 408mAh/g, and after 50 cycle periods, battery capacity is kept
Rate 93%.
The anode material of lithium-ion battery of the present invention can be applied to prepare Soft Roll sodium-ion battery, and sodium-ion battery compares
It is green, safe, cheap for lithium ion battery, there is very big advantage as stored energy application.
Brief description of the drawings
Fig. 1 is charging and discharging curve figure of the anode material of lithium-ion battery under different current densities made from embodiment 1；Its
In, A, a are that the charging and discharging curve under 20mA/g current densities, B, b are sodium-ion battery to anode material of lithium-ion battery respectively
The negative material charging and discharging curve under 200mA/g current densities respectively.
Fig. 2 is that the cycle performance test under 200mA/g current densities of anode material of lithium-ion battery made from embodiment 1 is bent
Line chart.
Fig. 3 is anode material of lithium-ion battery scanning electron microscope (SEM) photograph made from embodiment 1.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification selects.
Embodiment 1
The preparation method of anode material of lithium-ion battery：
(1) butter of tin and copper sulphate are weighed successively, and it is 0.4 to make the molar ratio of tin element and copper：0.6；Weigh
180~220nm of particle diameter titanium dioxide so that titanium elements molal quantity is equal to tin, copper molal quantity sum；Weigh single-layer graphene,
So that graphene quality is the 8% of tin element and copper gross mass；
Deionized water is used as dispersant, butter of tin and copper sulphate are configured to tin element and copper total concentration is
1mol/L, titanium dioxide, graphene are added, is uniformly dispersed, obtains mixed liquor；It is the heavy of 5mol/L that sodium hydroxide is configured into concentration
Shallow lake agent；
(2) precipitating reagent is at the uniform velocity added in the reactor containing mixed liquor, after carrying out hybrid reaction, ageing stands 12h, mistake
Filter, deionized water are washed 2 times, 100 DEG C of drying 10h, obtain presoma solid；
Wherein, the mixing speed of reactor is 500r/min, and the flow that precipitating reagent adds reactor is 4mL/min, mixing
The temperature of reaction is 50 DEG C, and the time of hybrid reaction is 2h, and the pH value of hybrid reaction is 11.5；
(3) mixed gas (volume ratio 5 of hydrogen and argon gas formed in hydrogen and argon gas：95) under atmosphere, by forerunner
Body solid sinters 5h in 600 DEG C, natural cooling, obtains anode material of lithium-ion battery.
Embodiment 2
The preparation method of anode material of lithium-ion battery：
(1) stannous chloride and copper sulphate are weighed successively, and it is 0.1 to make the molar ratio of tin element and copper：0.9；Weigh
Particle diameter 200nm or so titanium dioxide so that titanium elements molal quantity is equal to tin copper molal quantity sum；5~10 layer graphenes are weighed,
So that graphene quality is the 2% of tin element and copper gross mass；
Deionized water is used as dispersant, stannous chloride and copper sulphate are configured to tin element and copper total concentration is
2mol/L, titanium dioxide, graphene are added, is uniformly dispersed, obtains mixed liquor；It is the heavy of 1mol/L that sodium hydroxide is configured into concentration
Shallow lake agent；
(2) precipitating reagent is at the uniform velocity added in the reactor containing mixed liquor, after carrying out hybrid reaction, ageing stands 11h, mistake
Filter, deionized water are washed 2 times, 105 DEG C of drying 9h, obtain presoma solid；
Wherein, the mixing speed of reactor is 400r/min, and the flow that precipitating reagent adds reactor is 40mL/min, mixing
The temperature of reaction is 60 DEG C, and the time of hybrid reaction is 5h, and the pH value of hybrid reaction is 9.0；
(3) mixed gas (volume ratio 5 of hydrogen and argon gas formed in hydrogen and argon gas：95) under atmosphere, by forerunner
Body solid natural cooling, obtains anode material of lithium-ion battery after 700 DEG C sinter 2h.
Embodiment 3
The preparation method of anode material of lithium-ion battery：
(1) stannous chloride and copper chloride are weighed successively, and it is 0.3 to make the molar ratio of tin element and copper：0.7, weigh
Particle diameter 200nm or so titanium dioxide so that titanium elements molal quantity is equal to tin copper molal quantity sum；5~10 layer graphenes are weighed,
So that graphene quality is the 10% of tin element and copper gross mass；
Deionized water is used as dispersant, stannous chloride and copper chloride are configured to tin element and copper total concentration is
2mol/L, titanium dioxide, graphene are added, is uniformly dispersed, obtains mixed liquor；It is the heavy of 3mol/L that sodium hydroxide is configured into concentration
Shallow lake agent；
(2) precipitating reagent is at the uniform velocity added in the reactor containing mixed liquor, after carrying out hybrid reaction, ageing stands 13h, mistake
Filter, deionized water are washed 2 times, 95 DEG C of drying 9h, obtain presoma solid；
Wherein, the mixing speed of reactor is 800r/min, and the flow that precipitating reagent adds reactor is 100mL/min, is mixed
The temperature for closing reaction is 40 DEG C, and the time of hybrid reaction is 1h, and the pH value of hybrid reaction is 9.0；
(3) mixed gas (volume ratio 5 of hydrogen and argon gas formed in hydrogen and argon gas：95) under atmosphere, by forerunner
Body solid natural cooling, obtains anode material of lithium-ion battery after 500 DEG C sinter 5h.
Embodiment 4
The preparation method of anode material of lithium-ion battery：
(1) stannous chloride and copper sulphate are weighed successively, and it is 0.5 to make the molar ratio of tin element and copper：0.5；Weigh
Particle diameter 200nm or so titanium dioxide so that titanium elements molal quantity is equal to tin copper molal quantity sum；Single-layer graphene is weighed, is made
Obtain 8% that graphene quality is tin element and copper gross mass；
Deionized water is used as dispersant, stannous chloride and copper sulphate are configured to tin element and copper total concentration is
2mol/L, titanium dioxide, graphene are added, is uniformly dispersed, obtains mixed liquor；It is the heavy of 5mol/L that sodium hydroxide is configured into concentration
Shallow lake agent；
(2) precipitating reagent is at the uniform velocity added in the reactor containing mixed liquor, after carrying out hybrid reaction, ageing stands 11h, mistake
Filter, deionized water are washed 2 times, 100 DEG C of drying 11h, obtain presoma solid；
Wherein, the mixing speed of reactor is 600r/min, and the flow that precipitating reagent adds reactor is 40mL/min, mixing
The temperature of reaction is 60 DEG C, and the time of hybrid reaction is 5h, and the pH value of hybrid reaction is 10.5；
(3) mixed gas (volume ratio 5 of hydrogen and argon gas formed in hydrogen and argon gas：95) under atmosphere, by forerunner
Body solid natural cooling, obtains anode material of lithium-ion battery after 400 DEG C sinter 6h.
Comparative example 1
In comparative example 1, except the molar ratio of tin element and copper is 0.7：Outside 0.3, other parameters and process conditions are equal
As described in example 1 above, corresponding anode material of lithium-ion battery is prepared.
Comparative example 2
In comparative example 2, in addition to titanium dioxide is not added with, other parameters and process conditions as described in example 1 above, are prepared
Obtain corresponding anode material of lithium-ion battery.
Comparative example 3
Weigh 0.8mol SnCl4With 0.2mol CuSO45H2O is dissolved in 100mL deionized waters, adds 1.5mol
NaBH4, solution reduces immediately claims that SnCu alloys separate out, and collects precipitated product, washing and drying is stand-by.Again in mass ratio 7：2：
1 weighs SnCu alloys, SiC and graphite, and high-energy ball milling 6h produces product.Using the product as active material, metallic sodium piece is to electricity
Pole, 1molL-1NaPF6(EC-DEC=1:1) it is assembled into battery testing its electrochemistry system energy for electrolyte.In 100mAg-1Electric current is close
Degree, the discharge and recharge in the range of 0~2.0V, it is 420mAhg to measure first all reversible capacities-1, 360mAhg is maintained after circulating 20 weeks-1
Capacity, capability retention only has 85%, and cycle performance is poor.
Effect example 1
Anode material of lithium-ion battery prepared by embodiment 1 carries out ICP tests, and its test result is as shown in table 1.By table
1 understands that ICP test results show, anode material of lithium-ion battery made from embodiment 1 matches with its composition that feeds intake.(ICP
Model：The Radial of iCAP 6000, Thermo Fischer Scient Inc.)
Table 1
Similarly, the anode material of lithium-ion battery prepared by embodiment 2~4 carries out ICP tests, the results showed that, embodiment 2
~4 anode material of lithium-ion batteries prepared match with its respective composition that feeds intake.
Effect example 2
The anode material of lithium-ion battery of the preparation of 1.8g embodiments 1 is weighed, 0.1g carbon blacks is added and 0.1g is dissolved in N, N '-first
The Kynoar of base pyrrolidones, it is coated on after well mixed on aluminium foil and electrode slice is made.In the glove box of argon gas atmosphere,
Using metallic sodium piece as to electrode, Celgard2700 is barrier film, 1M NaClO4/PC：EMC(1：1) it is electrolyte, is assembled into button
Battery.
In 0.02~2.0V voltage ranges, charge-discharge test is carried out to battery.Fig. 1 is the sodium-ion battery negative pole of embodiment 1
Charge-discharge test curve map of the material under different current densities, wherein, A, a are that anode material of lithium-ion battery exists respectively
Charging and discharging curve under 20mA/g current densities, B, b are anode material of lithium-ion battery respectively under 200mA/g current densities
Charging and discharging curve.When current density is 20mA/g, the first circle discharge capacity of anode material of lithium-ion battery is higher than 590mAh/g；
When current density reaches 200mA/g, the first circle discharge capacity of anode material of lithium-ion battery reaches 408mAh/g, presents very
Good large current discharging capability.
Fig. 2 is that the cycle performance test under 200mA/g current densities of anode material of lithium-ion battery made from embodiment 1 is bent
Line chart.As shown in Figure 2, after 50 cycle periods, battery capacity conservation rate is more than 93%.According to method system described in embodiment 1
Make the button cell of the anode material of lithium-ion battery of embodiment 2~4, sodium piece be to electrode, it is close in 20mA/g, 200mA/g electric current
Under degree, capability retention after its first circle discharge capacity and circulation 50 times is tested respectively, specific data are as shown in table 2.
Table 2
To sum up, the anode material of lithium-ion battery for preparing of the present invention has higher charge/discharge capacity, preferably forthright again
Energy and cyclical stability.
Fig. 3 is anode material of lithium-ion battery scanning electron microscope (SEM) photograph made from embodiment 1.
Claims (21)
1. a kind of preparation method of anode material of lithium-ion battery, it is characterised in that it comprises the following steps：In reducing atmosphere
Under, after presoma is sintered, cooling, produce anode material of lithium-ion battery；
Wherein, the presoma is by by the mixed liquor containing graphene, titanium dioxide, pink salt and mantoquita, being mixed with precipitating reagent
Close the solid that reaction obtains；The mol ratio of tin element, copper and titanium elements is x：(1-x)：1,0<x≤0.5.
2. preparation method as claimed in claim 1, it is characterised in that the x is 0.1≤x≤0.5.
3. preparation method as claimed in claim 2, it is characterised in that the x is 0.3≤x≤0.5.
4. the preparation method as described in any one of claims 1 to 3, it is characterised in that the reducing atmosphere is hydrogen and argon
The mixed atmosphere of gas composition；
And/or the temperature of the sintering is 400~700 DEG C；The time of the sintering is 2~6 hours；
And/or the operation of the cooling is to naturally cool to room temperature.
5. preparation method as claimed in claim 4, it is characterised in that the reducing atmosphere is hydrogen and argon gas with 5：95
The mixed atmosphere of volume ratio composition.
6. the preparation method as described in any one of claims 1 to 3, it is characterised in that the graphene is 1~10 layer of graphite
Alkene；
And/or the particle diameter of the titanium dioxide is 50~400nm；
And/or the pink salt includes butter of tin and/or stannous chloride；
And/or the mantoquita includes copper sulphate and/or copper chloride.
7. preparation method as claimed in claim 6, it is characterised in that the graphene is single-layer graphene or 5~10 layers
Graphene.
8. preparation method as claimed in claim 6, it is characterised in that the dosage of the graphene is 2~10%, above-mentioned percentage
Than being graphene quality relative to tin element and the mass percent of copper gross mass.
9. preparation method as claimed in claim 6, it is characterised in that the particle diameter of the titanium dioxide is 180~220nm.
10. the preparation method as described in any one of claims 1 to 3, it is characterised in that solvent in the mixed liquor for go from
Sub- water；
And/or in the mixed liquor, the total concentration of pink salt and mantoquita is 1~2mol/L；
And/or the aqueous solution that the precipitating reagent is sodium hydroxide.
11. preparation method as claimed in claim 10, it is characterised in that the concentration of the precipitating reagent is 1~5mol/L.
12. the preparation method as described in any one of claims 1 to 3, it is characterised in that the presoma is by that described will sink
Shallow lake agent adds in the reactor containing the mixed liquor solid for carrying out hybrid reaction acquisition.
13. preparation method as claimed in claim 12, it is characterised in that the temperature of the reaction is 40~60 DEG C.
14. preparation method as claimed in claim 12, it is characterised in that the time of the reaction is 1~5 hour.
15. preparation method as claimed in claim 12, it is characterised in that the pH value of the reaction is 9.0~11.5.
16. preparation method as claimed in claim 12, it is characterised in that the mixing speed of the reactor is 400~800r/
min。
17. preparation method as claimed in claim 12, it is characterised in that the precipitating reagent add the flow of reactor for 4~
100mL/min。
18. the preparation method as described in any one of claims 1 to 3, it is characterised in that, will be described mixed after the hybrid reaction
The reaction solution for closing liquid and the precipitating reagent is aged, and is filtered, and is washed, and is dried, is obtained presoma solid.
19. preparation method as claimed in claim 18, it is characterised in that the ageing is to stand 11~13 hours；
And/or the washing is to be washed using deionized water；
And/or the number of the washing is twice；
And/or the operation of the drying is 95~105 DEG C and dried 9~11 hours.
A kind of 20. anode material of lithium-ion battery made from preparation method as described in any one of claim 1~19.
21. a kind of sodium-ion battery, it is characterised in that its negative pole includes sodium-ion battery negative pole material as claimed in claim 20
Material.
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