CN103378355A - Alkali metal secondary battery as well as negative active substance, negative material and negative electrode thereof, and preparation method of negative active substance - Google Patents

Alkali metal secondary battery as well as negative active substance, negative material and negative electrode thereof, and preparation method of negative active substance Download PDF

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CN103378355A
CN103378355A CN2012101071363A CN201210107136A CN103378355A CN 103378355 A CN103378355 A CN 103378355A CN 2012101071363 A CN2012101071363 A CN 2012101071363A CN 201210107136 A CN201210107136 A CN 201210107136A CN 103378355 A CN103378355 A CN 103378355A
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negative electrode
electrode active
negative
battery
alkali metal
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CN103378355B (en
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胡勇胜
王跃生
徐淑银
李泓
陈立泉
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Beijing Zhong Ke sea sodium Technology Co., Ltd.
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Institute of Physics of CAS
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    • YGENERAL 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
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses an alkali metal secondary battery as well as a negative active substance, a negative material and a negative electrode thereof, and a preparation method of the negative active substance. The chemical formula of the negative active substance is as follows: [A(x-y)By][Bx/3Ti(1-x/3)]O2-theta, wherein A and B respectively adopt one of potassium (K), sodium (Na) and lithium (Li), x is more than 0 and less than or equal to 1, y is more than or equal to 0 and less than x, and theta is more than or equal to 0 and less than or equal to 1. The negative active substance of the alkali metal secondary battery has single-phase reaction and has a voltage range of 0.5V to 1.2V in a sodium ion battery and a voltage range of 0.7V to 1.5V in a lithium ion battery, the deposition phenomenon of sodium metal on a negative electrode can be effectively avoided, and high capacity can be realized.

Description

The preparation method of the negative electrode active material of alkali metal secondary battery and usefulness thereof, negative material, negative pole and negative electrode active material
Technical field
The present invention relates to a kind of preparation method of negative material, negative material, negative pole and negative material of the titanate for alkali metal secondary battery, and the alkali metal secondary battery that adopts this negative material.
Background technology
Alkali metal secondary battery mainly comprises lithium rechargeable battery and sodium ion secondary battery etc.
Since the end of the eighties, Sony company produced first lithium ion battery, with its high-energy-density, long circulation life, the characteristics such as environmental pollution is little, on miniaturized electronics, be widely used, and begin in recent years to be applied to electric motor car and large-scale energy storage device.But along with the day by day consumption of lithium resource, people begin to turn one's attention to the more sodium of horn of plenty of resource, and are recently more and more to the research of sodium-ion battery.
From present report, the alkali metal secondary battery negative material mainly contains the graphitic carbon in alkali metal, the material with carbon element, amorphous and non-porous carbon black, carbon alloy and metal oxide.Alkali metal all easily produces metallic dendrite as negative material and the safety problems such as short circuit occur in charge and discharge cycles.As negative pole and self degree of graphitization and self property much relations are arranged for the graphite in the material with carbon element, amorphous carbon and specific area degree are very large.Alkali metal alloy is larger as the negative pole volumetric expansion, and cyclical stability is bad, moreover does not also find so far very good of good alloy cycle performance and capacity.Metal oxide is also a lot of as the problem of alkali metal secondary battery negative material, and it is large for example to discharge and recharge polarization, and it is unstable to circulate, and coulombic efficiency is low etc.
Now main practical cathode material lithium ion battery mainly concentrates on graphite material, for Li 4Ti 5O 12Then have the problems such as flatulence, and sodium-ion battery never has stable circulation, the negative material that coulombic efficiency is high.
Therefore, seeking that a kind of capacity is high, coulombic efficiency is high, good cycle, low-cost negative material, is that alkali metal secondary battery is in energy storage and the practical key of moving towards practicality.
Summary of the invention
The object of the present invention is to provide a kind of alkali metal secondary battery negative electrode active material with homogeneous reaction and preparation method thereof, it is lower and easily form the defective of alkali metal deposition to overcome present alkali metal secondary battery negative material current potential.
Another object of the present invention is to provide negative material, negative pole and the alkali metal secondary battery that adopts this negative material.
The invention provides a kind of alkali metal secondary battery negative electrode active material, the chemical formula of this negative electrode active material is: [A (x-y)B y] [B X/3Ti (1-x/3)] O 2-δ, wherein, A, B adopt respectively wherein a kind of of K, Na and Li; 0<x≤1,0≤y<x, 0≤δ≤1.
Preferably, A is Na, and B is Li; 0.5≤x≤0.8,0≤y<x, 0≤δ≤0.1.
The present invention also provides the preparation method of described negative electrode active material, and described preparation method can be selected from any in solid phase method and the sol-gel process.
Described sol-gel process comprises the steps:
1) stoichiometric proportion according to negative electrode active material takes by weighing an amount of alkali-metal acetate and butyl titanate and is dissolved in respectively absolute ethyl alcohol, ethanol solution with alkali metal acetic acid in whipping process slowly joins in the ethanol solution of butyl titanate, and the adding citric acid, form aqueous precursor gel;
2) the gained aqueous precursor gel is placed crucible in 250-500 ℃ of preliminary treatment two hours, 750-1000 ℃ of lower the processing 8~20 hours, grind and namely get described negative electrode active material again.
Described solid phase method comprises the steps:
1) with alkali-metal carbonate, titanyl compound, mix according to the stoichiometric proportion of negative electrode active material, after grinding evenly precursor powder;
2) the gained precursor powder is placed in the crucible in 650~1000 ℃ of lower processing 8~25 hours, grind and namely get described negative electrode active material.
Preparation in accordance with the present invention, wherein, can adopt in the following methods any that described negative electrode active material is coated one or more of carbon-coating, metal level, nitride layer, oxide skin(coating) and high polymer layer: (1) adds sucrose, glucose, organic polymer, ionic liquid or slaine in described precursor powder or gel, and at Ar or N 2Heat treated under the inert gas shielding; (2) in described negative electrode active material, add sucrose, glucose, organic polymer, ionic liquid or slaine, and at Ar or N 2Heat treated under the Buchholz protection; (3) adopt the thermal vapor deposition method that described presoma or described negative electrode active material are coated.
The invention provides a kind of alkali metal secondary battery negative material, described negative material can comprise conductive additive and binding agent, the negative electrode active material that can also comprise negative electrode active material of the present invention or make according to preparation method of the present invention.
The invention provides a kind of alkali metal secondary battery negative pole, described negative pole can comprise negative material of the present invention and collector.
The invention provides a kind of alkali metal secondary battery, described alkali metal secondary battery can comprise anodal and negative pole of the present invention, and places the electrolyte between described positive pole and the described negative pole.
Described negative electrode active material during for the preparation of alkali metal secondary battery negative material and negative pole, can be adopted the general manufacture method of existing lithium ion battery or sodium-ion battery.That is, with negative electrode active material of the present invention with as the powder of conductive additive (such as carbon black, acetylene black, graphite powder, carbon nano-tube, graphite rare etc.) ground and mixed, described conductive additive accounts for 0~30wt%.Then with general binder solution (PVDF (polyvinylidene fluoride), Sodium alginate (sodium alginate), CMC (sodium carboxymethylcellulose), SBR (butadiene-styrene rubber) etc.), for example can be NMP (1-METHYLPYRROLIDONE) solution of PVDF (polyvinylidene fluoride), be mixed into uniform sizing material, be coated on (such as Copper Foil, titanium foil, nickel screen, nickel foam etc.) preparation electrode slice on the collector, the thickness of gained film can be 2~500 μ m after applying.The electrode obtained sheet is cut into suitable shape, and 100~150 ℃ of lower oven dry are rear for subsequent use in being essentially the environment of vacuum.
Improvements in the described alkali metal secondary battery are to use negative electrode active material provided by the invention, and other part and preparation method are conventionally known to one of skill in the art, repeat no more herein.Described alkali metal secondary battery can be water system, non-water or all solid state alkali metal secondary battery.
Sodium-ion battery in the alkali metal secondary battery of the present invention have cost low, have extended cycle life, the energy density high, can be widely used in solar energy, the required extensive energy storage device of wind power generation, and the field such as intelligent grid peak regulation, distribution power station, back-up source, communication base station, especially be suitable as extensive energy storage device.
The negative electrode active material of alkali metal secondary battery of the present invention has homogeneous reaction, in sodium-ion battery between voltage range 0.5~1.2V, voltage range 0.7-1.5V in lithium ion battery, the phenomenon that can effectively avoid the sodium metal to deposit at negative pole also has higher capacity (first all discharge capacities are greater than 120mAh/g under C/10).
Description of drawings
Below, describe by reference to the accompanying drawings embodiment of the present invention in detail, wherein:
Fig. 1 shows X-ray diffraction (XRD) collection of illustrative plates of the negative electrode active material of the embodiment of the invention 1;
Fig. 2 shows ESEM (SEM) figure of the negative electrode active material of the embodiment of the invention 1;
Fig. 3 shows front 5 all charging and discharging curves of the sodium-ion battery of the embodiment of the invention 1;
Fig. 4 shows front 4 all charging and discharging curves of the lithium ion battery of the embodiment of the invention 2;
Fig. 5 shows the not carbon coated of the embodiment of the invention 3 and the charging and discharging curve of carbon coated sodium-ion battery.
Fig. 6 shows first all charging and discharging curves of the sodium-ion battery of the embodiment of the invention 4;
Fig. 7 shows first all charging and discharging curves of the lithium ion battery of the embodiment of the invention 5.
Embodiment
Further specify the present invention below by specific embodiment, still, should be understood to, these embodiment are only used for the more detailed usefulness that specifically describes, and should not be construed as for limiting in any form the present invention.
General description is carried out to the material and the test method that use in the present invention's test in this part.Although for realizing that the employed many materials of the object of the invention and method of operation are well known in the art, the present invention still does to describe in detail as far as possible at this.It will be apparent to those skilled in the art that in context, if do not specify that material therefor of the present invention and method of operation are well known in the art.
Embodiment 1
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
Present embodiment adopts solid phase method to prepare negative electrode active material Na 0.66Li 0.22Ti 0.78O 2, concrete steps are: with nano-anatase TiO 2(grain diameter is 50~100nm), Li 2CO 3(analyzing pure) and Na 2CO 3Mix by stoichiometric proportion, obtain presoma mixed grinding half an hour in agate mortar, to the gained presoma at the 20MPa compressing tablet, gained disk diameter 1.5cm, thickness 0.4cm transfers to Al with the presoma sheet 2O 3In the crucible, 1000 ℃ of lower processing 20 hours in Muffle furnace, gained white powder sheet is for subsequent use after grinding, and is negative electrode active material Na of the present invention 0.66Li 0.22Ti 0.78O 2, its XRD collection of illustrative plates and SEM figure see Fig. 1 and Fig. 2.Can be found out that by Fig. 1 and Fig. 2 this negative electrode active material is that particle diameter is the particle of 2~10 μ m, and is Na 0.66Li 0.22Ti 0.78O 2Pure phase.
Above-mentioned negative electrode active material is prepared into sodium-ion battery.Concrete steps are: with the negative electrode active material Na for preparing 0.66Li 0.22Ti 0.78O 2Powder mixes according to 60: 30: 10 weight ratio with acetylene black, binding agent PVDF, add an amount of nmp solution, in the environment of air drying, grind and form slurry, then slurry evenly is coated on copper foil of affluxion body or the aluminium foil, be cut into the pole piece of 8 * 8mm after the drying, in 100 ℃ of dryings 10 hours, it was for subsequent use to be transferred to immediately glove box under vacuum condition.Carry out in the glove box that is assemblied in Ar atmosphere of simulated battery, with the sodium metal sheet as to electrode, the NaClO of 1M 4/ PC (propylene carbonate) solution is assembled into the CR2032 button cell as electrolyte.Use the constant current charge-discharge pattern to test, discharge is 0V by voltage, and charging is 3.0V by voltage, and all tests are all carried out under the C/10 current density.Test result is seen Fig. 3, and wherein a1, a2, b1, b2 are respectively first all charging curves, first all discharge curves, the 5th all charging curves, the 5th all discharge curves.Found out that by Fig. 3 its first all discharge capacity can reach 290mAh/g, first all coulombic efficiencies are about 62%, and the charge and discharge current potential is about 0.5~1.2V.
Embodiment 2
Present embodiment is used for illustrating that negative electrode active material of the present invention is in the application of lithium ion battery.
Present embodiment adopts embodiment 1 solid phase method to prepare negative electrode active material Na 0.66Li 0.22Ti 0.78O 2
Above-mentioned negative electrode active material is prepared into lithium ion battery.Concrete steps are: with the negative electrode active material Na for preparing 0.66Li 0.22Ti 0.78O 2Powder mixes according to 60: 30: 10 weight ratio with acetylene black, binding agent PVDF, add an amount of nmp solution, in the environment of air drying, grind and form slurry, then evenly be coated on slurry on the copper foil of affluxion body, be cut into the pole piece of 8 * 8mm after the drying, in 100 ℃ of dryings 10 hours, it was for subsequent use to be transferred to immediately glove box under vacuum condition.Carry out in the glove box that is assemblied in Ar atmosphere of simulated battery, with metal lithium sheet as to electrode, the LiBF of 1M 6/ PC solution is assembled into the CR2032 button cell as electrolyte.Use the constant current charge-discharge pattern to test, discharge is 0V by voltage, and charging is 3.0V by voltage, and all tests are all carried out under the C/10 current density.Test result is seen Fig. 4, and wherein c1, c2, d1, d2 are respectively first all charging curves, first all discharge curves, 4th week charging curve, 4th week discharge curve.Found out that by Fig. 3 its first all discharge capacity can reach 440mAh/g, first all coulombic efficiencies are about 75%, and the charge and discharge current potential is about 0.8~1.5V.
Embodiment 3
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
Present embodiment adopts sol-gel process to prepare negative electrode active material Na 0.66Li 0.22Ti 0.78O 2, and it is carried out the carbon coating process.Concrete steps are: with butyl titanate (Ti (C 4H 9O) 4), lithium acetate (CH 3COOLi) sodium acetate ((CH 3COONa) take by weighing in right amount according to stoichiometric proportion, and be dissolved in respectively absolute ethyl alcohol.Ethanol solution with lithium acetate in whipping process joins in the ethanol solution of carbonic acid four butyl esters gradually, and adds an amount of citric acid to suppress hydrolysis, forms gradually aqueous precursor gel, and the gained aqueous precursor gel is transferred to Al 2O 3In 900 ℃ of lower processing 20 hours, it is for subsequent use to obtain white powder after the grinding in the crucible.With this white powder and ionic liquid [EMIm] [N (CN) 2] (1-ethyl-3-methy limidazoliumdicyanamide) mix, and in Ar atmosphere, carry out pyrolysis in 600 ℃ of heating 4h, namely obtain the negative electrode active material Na that carbon coats after the cooling 0.66Li 0.22Ti 0.78O 2/ C, wherein the thickness of nitrogen-doped carbon layer is essentially 1~10nm.Also can use other feasible methods that described negative electrode active material is coated carbon-coating, perhaps covered with metal layer, nitride layer, oxide skin(coating) and high polymer layer etc. herein.
The negative electrode active material that above-mentioned carbon is coated is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are carried out the C/10 discharge with embodiment 1 to battery, and test result is seen Fig. 5, and wherein e1, e2 are respectively first all charging curves and first all discharge curves, and f1 and f2 do not wrap carbon to process.As seen from Figure 5, first all coulombic efficiencies have brought up to 80% by not wrapping 68% of carbon.
Embodiment 4
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
Present embodiment adopts solid phase method to prepare negative electrode active material Na 0.51Li 0.17Ti 0.83O 2, concrete steps are: with TiO 2, Li 2CO 3And Na 2CO 3Mix according to stoichiometric proportion, 900 rev/mins of dry grinding mixed 4 hours in agate jar, obtained the precursor powder of white; With the pressure lower sheeting of gained powder at 20MPa, gained presoma sheet is transferred to Al 2O 3In the crucible, 1000 ℃ of heat treatment is 15 hours under air atmosphere, and the gained sheet obtains powder after grinding for subsequent use, is negative electrode active material Na of the present invention 0.51Li 0.17Ti 0.83O 2
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.The test voltage scope is 0.4V-2.5V, and test result is seen Fig. 6.Fig. 6 is first all charging and discharging curves.As seen from Figure 6, its first all discharge capacity can reach 147mAh/g, and first all coulombic efficiencies are about 73.5%, and capacity is 108mAh/g after five weeks of circulation.
Embodiment 5
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The material that present embodiment adopts embodiment 4 to be synthesized is dressed up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.The voltage tester scope is 0.7-2.5V, and test result is seen Fig. 7, and its first all discharge capacity can reach 223mAh/g, and first all coulombic efficiencies are about 69%, and capacity is 153mAh/g after five weeks of circulation.
Embodiment 6
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
Present embodiment adopts solid phase method to prepare negative electrode active material Na 0.54Li 0.18Ti 0.82O 2, concrete steps are: with nano-anatase TiO 2(grain diameter is 50~100nm), Li 2CO 3(analyzing pure) and Na 2CO 3Mix by stoichiometric proportion, obtain presoma mixed grinding half an hour in agate mortar, precursor powder is transferred to Al 2O 3In the crucible, 1000 ℃ of lower 20h that process in Muffle furnace, gained white powder sheet is for subsequent use after grinding, and is negative electrode active material Na of the present invention 0.54Li 0.18Ti 0.82O 2
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.The test voltage scope is 0.4V-2.5V, the results are shown in following table 1.
Embodiment 7
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The material that present embodiment adopts embodiment 6 to be synthesized is dressed up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Test result sees Table 1.
Embodiment 8
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
Present embodiment adopts solid phase method to prepare negative electrode active material Na 0.6Li 0.2Ti 0.8O 2, concrete steps are: with nano-anatase TiO 2(grain diameter is 50~100nm), Li 2CO 3(analyzing pure) and Na 2CO 3Mix by stoichiometric proportion, obtain presoma mixed grinding half an hour in agate mortar,, precursor powder is transferred to Al 2O 3In the crucible, 1000 ℃ of lower processing 20 hours in Muffle furnace, gained white powder sheet is for subsequent use after grinding, and is negative electrode active material Na of the present invention 0.6Li 0.2Ti 0.8O 2
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.The test voltage scope is 0.4V-2.5V, the results are shown in following table 1.
Embodiment 9
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The material that present embodiment adopts embodiment 8 to be synthesized is dressed up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.Test result sees Table 1.
Embodiment 10
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
Present embodiment adopts solid phase method to prepare negative electrode active material Na 0.75Li 0.25Ti 0.75O 2, concrete steps are: with nano-anatase TiO 2(grain diameter is 50~100nm), Li 2CO 3(analyzing pure) and Na 2CO 3Mix by stoichiometric proportion, obtain presoma mixed grinding half an hour in agate mortar, precursor powder is transferred to Al 2O 3In the crucible, 1000 ℃ of lower 20h that process in Muffle furnace, gained white powder sheet is for subsequent use after grinding, and is negative electrode active material Na of the present invention 0.75Li 0.25Ti 0.75O 2
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.The test voltage scope is 0.4V-2.5V, the results are shown in following table 1.
Embodiment 11
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The material that present embodiment adopts embodiment 10 to be synthesized is dressed up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 2.Test result sees Table 1.
Embodiment 12
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
Present embodiment adopts sol-gel process to prepare negative electrode active material Na 0.81Li 0.27Ti 0.73O 2, and it is carried out the carbon coating process.Concrete steps are: with butyl titanate (Ti (C 4H 9O) 4), lithium acetate (CH 3COOLi) sodium acetate ((CH 3COONa) take by weighing in right amount according to stoichiometric proportion, and be dissolved in respectively absolute ethyl alcohol.Ethanol solution with lithium acetate in whipping process joins in the ethanol solution of carbonic acid four butyl esters gradually, and adds an amount of citric acid to suppress hydrolysis, forms gradually aqueous precursor gel, and the gained aqueous precursor gel is transferred to Al 2O 3In 900 ℃ of lower processing 20 hours, it is for subsequent use to obtain white powder after the grinding in the crucible.Be negative electrode active material Na of the present invention 0.81Li 0.27Ti 0.73O 2
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.The test voltage scope is 0.5V-2.5V, the results are shown in following table 1.
Embodiment 13
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The material that present embodiment adopts embodiment 12 to be synthesized is dressed up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 2.Test result sees Table 1.
Embodiment 14
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
Present embodiment adopts solid phase method to prepare negative electrode active material [Na 2/7Li 1/7] [Li 1/7Ti 2/7] O 2Concrete steps are: with nano-anatase TiO 2(grain diameter is 50~100nm), Li 2CO 3(analyzing pure) and Na 2CO 3Mix by stoichiometric proportion, obtain presoma mixed grinding half an hour in agate mortar,, precursor powder is transferred to Al 2O 3In the crucible, 1000 ℃ of lower 15h that process in Muffle furnace, gained white powder sheet is for subsequent use after grinding, and is negative electrode active material [Na of the present invention 2/7Li 1/7] [Li 1/7Ti 2/7] O 2
Above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 2.The test voltage scope is 0.7V-2.5V, the results are shown in following table 1.
Embodiment 15
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
Present embodiment adopts solid phase method to prepare negative electrode active material Na 0.77Li 0.31Ti 0.73O 1.97Concrete steps are: with nano-anatase TiO 2(grain diameter is 50~100nm), Li 2CO 3(analyzing pure) and Na 2CO 3Mix by stoichiometric proportion, obtain presoma mixed grinding half an hour in agate mortar,, precursor powder is transferred to Al 2O 3In the crucible, 950 ℃ of lower processing 18 hours in Muffle furnace, gained white powder sheet is for subsequent use after grinding, and is negative electrode active material Na of the present invention 0.77Li 0.31Ti 0.73O 1.97
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.The test voltage scope is 0.3V-2.5V, the results are shown in following table 1.
Embodiment 16
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The material that present embodiment adopts embodiment 13 to be synthesized is dressed up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 2.Test result sees Table 1.
Embodiment 17
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
Present embodiment adopts sol-gel process to prepare negative electrode active material Na 0.69Li 0.23Ti 0.77O 1.99Concrete steps are: with butyl titanate (Ti (C 4H 9O) 4), lithium acetate (CH 3COOLi) sodium acetate ((CH 3COONa) take by weighing in right amount according to stoichiometric proportion, and be dissolved in respectively absolute ethyl alcohol.Ethanol solution with lithium acetate in whipping process joins in the ethanol solution of carbonic acid four butyl esters gradually, and adds an amount of citric acid to suppress hydrolysis, forms gradually aqueous precursor gel, and the gained aqueous precursor gel is transferred to Al 2O 3In 850 ℃ of lower processing 25 hours, it is for subsequent use to obtain white powder after the grinding in the crucible.Be negative electrode active material Na of the present invention 0.69Li 0.23Ti 0.77O 1.99
Above-mentioned negative electrode active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 1.The test voltage scope is 0.5V-2.5V, the results are shown in following table 1.
Embodiment 18
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The material that present embodiment adopts embodiment 17 to be synthesized is dressed up lithium ion battery, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its preparation process and method of testing are with embodiment 2.Test result sees Table 1.
Embodiment 19
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The active material that present embodiment adopts embodiment 17 to be synthesized utilizes the Al of ald (ALD) 2nm 2O 3, above-mentioned negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its method of testing is with embodiment 2.Test result sees Table 1.
Embodiment 20
Present embodiment is used for illustrating preparation and the application thereof of negative electrode active material of the present invention.
The active material that present embodiment adopts embodiment 17 to be synthesized; directly with above-mentioned material and PAM (polyacrylamide) according to mixing in 6%: 94%; be so incensed that at Ar 750 degree are processed in the protective atmosphere; obtain the compound of nitrogen-doped carbon; the gained negative electrode active material is prepared into lithium ion battery, and carries out electro-chemical test.Its method of testing is with embodiment 2.Test result sees Table 1.
Although the present invention has carried out description to a certain degree, significantly, under the condition that does not break away from the spirit and scope of the present invention, can the suitable variation of each condition of carrying out.Be appreciated that to the invention is not restricted to described embodiment, and be attributed to the scope of claim, it comprises the replacement that is equal to of described each factor.

Claims (7)

1. negative electrode active material, chemical formula is: [A (x-y)B y] [B X/3Ti (1-x/3)] O 2-δ, wherein, A, B adopt respectively wherein a kind of of K, Na and Li; 0<x≤1,0≤y<x, 0≤δ≤1.
2. negative electrode active material as claimed in claim 1, wherein, A is Na, B is Li; 0.5≤x≤0.8,0≤y<x, 0≤δ≤0.1.
3. negative electrode active material as claimed in claim 2, wherein, described negative electrode active material is coated with one or more in carbon-coating, metal level, nitride layer, oxide skin(coating) and the high polymer layer; Wherein, the thickness of described carbon-coating, metal level, nitride layer, oxide skin(coating) and high polymer layer is 1~10nm independently of one another.
4. negative material, described negative material comprises: the arbitrary described negative electrode active material of conductive additive, binding agent and employing such as claim 1~3.
5. negative pole, described negative pole comprises negative material claimed in claim 4 and collector.
6. alkali metal secondary battery, described alkali metal secondary battery comprise anodal and negative pole claimed in claim 5, and place the electrolyte between described positive pole and the described negative pole.
7. the preparation method of a negative electrode active material, described preparation method can be selected from any in solid phase method and the sol-gel process:
Described sol-gel process comprises the steps:
1) stoichiometric proportion according to negative electrode active material takes by weighing an amount of alkali-metal acetate and butyl titanate and is dissolved in respectively absolute ethyl alcohol, ethanol solution with alkali metal acetic acid in whipping process slowly joins in the ethanol solution of butyl titanate, and the adding citric acid, form aqueous precursor gel;
2) the gained aqueous precursor gel is placed crucible in 250-500 ℃ of preliminary treatment two hours, 750-1000 ℃ of lower the processing 8~20 hours, grind and namely get described negative electrode active material again;
Described solid phase method comprises the steps:
1) with alkali-metal carbonate, titanyl compound, mix according to the stoichiometric proportion of negative electrode active material, after grinding evenly precursor powder;
2) the gained precursor powder is placed in the crucible in 650~1000 ℃ of lower processing 8~25 hours, grind and namely get described negative electrode active material.
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CN109244441A (en) * 2018-08-29 2019-01-18 浙江大学 Non-newtonian flow posture Na-K alloy electrode and its preparation method and application
CN109244441B (en) * 2018-08-29 2020-06-05 浙江大学 non-Newtonian fluid Na-K alloy electrode and preparation method and application thereof

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