CN108172780A - A kind of alkali metal secondary battery negative electrode active material and preparation method thereof - Google Patents
A kind of alkali metal secondary battery negative electrode active material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to field of electrochemical power source, and in particular to a kind of alkali metal secondary battery negative electrode active material and preparation method thereof.The negative electrode active material is the spherical nucleocapsid coated entirely, and shell is nano-titanium dioxide, and core includes nanometer di-iron trioxide；The mass ratio of ferro element and titanium elements is 5 15：1.The material uniqueness nucleocapsid helps to alleviate the volume expansion in charge and discharge process, keeps the structural stability of active material in cyclic process.Generated in-situ nano iron particles help to improve the electronic conductance of material simultaneously, accelerate the electronics transfer between active material particle.The material has both the multiple features such as high power capacity, high circulation stability in the case where not introducing conductive agent carbon source, is a kind of cheap and environmental-friendly novel energy storage cell negative electrode active material as alkali metal secondary battery negative electrode active material.
Description
Technical field
The invention belongs to field of electrochemical power source, and in particular to a kind of alkali metal secondary battery negative electrode active material and its system
Preparation Method.
Background technology
In recent years, with the popularization of the energy storage systems such as electric vehicle, intelligent grid, people are for high-energy density secondary electricity
The demand of pond body system is more urgent.Alkali metal secondary battery mainly includes lithium rechargeable battery and sodium ion secondary battery etc..
Lithium rechargeable battery has many advantages, such as high voltage, high power capacity, high power density, has extended cycle life and memory-less effect, just
It is general to take being widely used for the fields such as formula electronic equipment, electric vehicle, national defense industry and portable electronic device.But lithium ion two
Primary cell is there are the problems such as of high cost, short life and security risk, in addition, the storage of lithium resource is very limited, largely
On limit the large-scale application of lithium rechargeable battery.
The research of sodium ion secondary battery almost starts to walk simultaneously with lithium rechargeable battery, but its development is extremely difficult.It is early
In last century the eighties, people have just carried out the research of sodium ion secondary battery positive and negative pole material, but almost all of taste
Examination is come to an end with disappointed.This is mainly due to positive and negative pole material system of the early stage in relation to storage sodium reaction simply to transplant lithium mostly
The material structure being applied successfully in ion secondary battery, without fully considering storage sodium reaction for the special of host lattice structure
It is required that.
Report that main alkali metal secondary battery negative material mainly has alkali metal, amorphous carbon material, graphitic carbon at present
Material, alkali metal alloy and metal oxide.Alkali metal easily generates branch as negative material during charge and discharge cycles
Crystalline substance, so as to cause safety problems such as short circuits.When graphitic carbon material is as lithium ion secondary battery negative pole, chemical property and graphite
Change degree has much relations, and graphite cannot act as the Carbon anode of sodium-ion battery due to the problem of interlamellar spacing.Amorphous carbon materials
The storage sodium effect of material is best, but specific surface area degree has a significant impact to chemical property.Alkali metal alloy is as the secondary electricity of alkali
Volume expansion is big during the cathode of pond, causes cyclical stability bad.Also there is volume as alkaline secondary battery cathode in metal oxide
Expansion is serious, and electronic conductance is low, recycles the problem of unstable.
Titanium dioxide is a kind of potential alkali metal secondary battery negative material, since its operating voltage is low, chemistry
Stability is good, and natural abundance is high, at low cost.Titanium dioxide has the structure in multidimensional tunnel, can be embedded in alkali metal ion, as
Negative material, the TiO of different tunnel structures2Show different embedding sodium or embedding lithium property.J.Huang(J.P.Huang,
D.Yuan,H.Z.Zhang,Y.L.Cao,G.R.Li,H.X.Yang,X.P.Gao,Electrochemical sodium
storage of TiO2(B)nanotubes for sodium ion batteries[J],RSC Advances,3(2013)
12593-12597.) etc. be prepared for the monoclinic phase TiO of stratiform2(B) nanotube, (001) crystal face have the interlamellar spacing of 0.56nm,
It is suitble to the embedded abjection of sodium ion, there is 80mAh g in 3.0-0.8V-1Reversible specific capacity.L.Wu(L.M.Wu,
D.Bresser,D.Buchholz,G.A.Giffin,C.R.Castro,A.Ochel,S.Passerini,Unfolding the
Mechanism of Sodium Insertion in Anatase TiO2Nanoparticles[J],Adv.Energy
Mater., 5 (2015) 1401142.) etc. be prepared for anatase TiO2, can realize 0.41Na (140mAh g-1) it is embedding de-, but
Low ion diffusion rates and low intrinsic electronic conductivity limit its performance.In addition, during removal lithium embedded, anatase titanium dioxide
Titanium is considered a kind of zero strain material.And transition metal oxide, such as ferroso-ferric oxide, it is a kind of secondary with conversion reaction
Battery cathode, has the features such as theoretical capacity is high, environmental-friendly, but because of it in the electrochemical reaction of removal lithium embedded or deintercalation sodium body
The problem of product expansion structure caves in, leads to poor circulation.Therefore, find a kind of stable structure, capacity are high, coulombic efficiency is high,
Good, the cheap negative material of stable circulation performance is the key that alkali metal secondary battery in energy storage and practical application.
Invention content
In view of this, one of the objects of the present invention is to provide a kind of alkali metal secondary battery negative electrode active materials.It is described
Negative electrode active material has stable nucleocapsid, and outer layer titanium dioxide can play volume change in caching charge and discharge process
Effect improves the cyclical stability of alkali metal secondary battery.Meanwhile generated in-situ nanometer di-iron trioxide is sintered in air
Particle and nano iron particles improve the electronic conductance of material, solve the problems, such as that material high rate performance is poor.
The second object of the present invention is to provide a kind of preparation method of alkali metal secondary battery negative electrode active material, the party
Method is coagulated using the environmental-friendly back flow reaction easy to operate easily realized and the colloidal sol of hydro-thermal reaction and in-stiu coating titanium dioxide
Glue process is formed by presoma low-temperature sintering with the material for stablizing nucleocapsid.
To achieve the above object, technical scheme is as follows：
A kind of alkali metal secondary battery negative electrode active material, the negative electrode active material are the spherical nucleocapsid knot coated entirely
Structure, shell are nano-titanium dioxide, and core includes nanometer di-iron trioxide；The mass ratio of ferro element and titanium elements is 5-15：1.
Preferably, the spherical particle size of the negative electrode active material is 200-300nm.
Preferably, the nano-titanium dioxide shell is impalpable structure or anatase structured.
Preferably, the thickness of the nano-titanium dioxide shell is 5-100nm.
Preferably, core is nanometer di-iron trioxide and the mixture of nano iron particles, and nano iron particles are distributed in core most
Outer layer.
A kind of preparation method of alkali metal secondary battery negative electrode active material of the present invention, the method step is such as
Under：
(1) surfactant is dissolved in ethylene glycol, surfactant concentration is：0.1-2g/L, magnetic agitation 30-
360min is allowed to dissolve；Under magnetic agitation, molysite is added in, continues stirring to a period of time is completely dissolved, obtains mixed solution 1；
(2) by mixed solution 1 at 60-220 DEG C back flow reaction 30-360min, mixing speed 200-1200r/min,
After reaction, the hydro-thermal reaction 6-24h at 120-180 DEG C, centrifugation, after precipitation is washed with ethyl alcohol, 60-80 DEG C of drying obtains
Granular precursor；
(3) titanium salt is dissolved in ethyl alcohol, the mass ratio of titanium salt and ethyl alcohol is 1:4-8 obtains mixed solution 2；
(4) granular precursor that step (2) obtains is dissolved in mixed solution 2, the matter of granular precursor and mixed solution 2
Amount is than being 3-10:1,60-120 DEG C of stirring is volatilized completely to ethyl alcohol, obtains intermediate product；
(5) intermediate product is sintered 1-6h at 300-600 DEG C, heating rate is 1-5 DEG C/min, obtains a kind of alkali metal
The negative electrode active material of secondary cell.
Preferably, the surfactant is polyvinylpyrrolidone-K30 (PVP-K30), cetyl trimethyl bromination
Ammonium (CTAB) or ethylenediamine tetra-acetic acid (EDTA).
Preferably, the molysite is Fe (NO3)3·9H2O or FeCl3。
Preferably, the titanium salt is isopropyl titanate, butyl titanate or titanium tetrachloride.
A kind of sodium ion secondary battery, the negative electrode active material of the battery are secondary for a kind of alkali metal of the present invention
The negative electrode active material of battery.
A kind of lithium rechargeable battery, the negative electrode active material of the battery are secondary for a kind of alkali metal of the present invention
The negative electrode active material of battery.
Advantageous effect
1. the present invention provides a kind of negative electrode active material of alkali metal secondary battery, zero strain nano titania shell is equal
Even cladding nanometer ferric oxide particle, forms two-dimentional nucleocapsid, further, generated in-situ nanometer during thermal sintering
Iron particle is evenly distributed on the outside of ferric oxide nanometer particle, forms three-dimensional nucleocapsid.This unique two dimension or three-dimensional nucleocapsid
Structure helps to alleviate the volume expansion in charge and discharge process, keeps the structural stability of active material in cyclic process.Simultaneously
Generated in-situ nanometer di-iron trioxide and nano iron particles help to improve the electronic conductance of material, accelerate active material particle
Between electronics transfer.The material is as alkali metal secondary battery negative electrode active material, in the feelings for not introducing conductive agent carbon source
The multiple features such as high power capacity, high circulation stability are had both under condition, are a kind of cheap and environmental-friendly novel energy storage cells
Negative electrode active material.
2. the present invention provides a kind of preparation method of the negative electrode active material of alkali metal secondary battery, flowed back by controlling
Temperature and return time and hydrothermal temperature and time, in-situ preparation spherical iron oxide precursor.In reaction process, reflux temperature
Degree control is at 60-220 DEG C, reflux time 30-360min；Temperature is excessively high, and the reaction time is too short, and it is uniform can not to obtain pattern
Surfactant complexing spherical precursor particle；The temperature too low reaction time is long, and surfactant cannot occur uniformly
Stable complex reaction, granular precursor are reunited serious.Hydrothermal temperature control is at 120-180 DEG C, the hydro-thermal reaction time 6-
For 24 hours, when the temperature too low time is too short ferric oxide nanometer particle growth it is uneven, when the temperature is excessively high between long, the iron oxide of growth
Nanoparticle agglomerates are serious；The uniform spherical precursor particle of homodisperse pattern can not all be obtained.In back flow reaction and colloidal sol
It is to obtain the important step of stable spherical structure that hydro-thermal reaction is added in gel reaction process.The raw material that the method uses are equal
For widely distributed in nature, cheap and environmental-friendly substance, preparation means are simple, of low cost, environmentally protective,
Material property is more stablized, it is easy to accomplish produces in enormous quantities.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram of granular precursor made from embodiment 1.
Fig. 2 is the ferro element distribution map of alkali metal secondary battery negative electrode active material made from embodiment 1.
Fig. 3 is the ferro element distribution map of alkali metal secondary battery negative electrode active material made from embodiment 1.
Fig. 4 is the titanium elements distribution map of alkali metal secondary battery negative electrode active material made from embodiment 1.
Fig. 5 is the oxygen element distribution map of alkali metal secondary battery negative electrode active material made from embodiment 1.
Fig. 6 is the transmission electron microscope figure of alkali metal secondary battery negative electrode active material made from embodiment 1.
Fig. 7 is the X-ray diffraction spectrogram of alkali metal secondary battery negative electrode active material made from embodiment 1.
Fig. 8 is 20 weeks charging and discharging curves before sodium ion secondary battery in embodiment 1.
Fig. 9 is sodium ion secondary battery high rate performance figure in embodiment 1.
Figure 10 is 20 weeks charging and discharging curves before lithium rechargeable battery in embodiment 1.
Figure 11 is lithium rechargeable battery high rate performance figure in embodiment 1.
Figure 12 is sodium ion secondary battery cycle performance figure in embodiment 2.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail.
The assembling of alkali metal secondary battery：
(1) assembling of sodium ion secondary battery：
The final product that embodiment is prepared is with acetylene black, binding agent polyvinylidene fluoride (PVDF) according to 8:1:1
Weight ratio mix, add in N-Methyl pyrrolidone (NMP) solution, in the environment of air drying grinding form slurry, then
Slurry is evenly applied on copper foil of affluxion body, and the electrode slice of a diameter of 1cm, under vacuum 80 DEG C of dryings are cut into after dry
After 12h, it is spare to be transferred to glove box.Button cell is using metallic sodium as electrode, by NaPF6It is dissolved in ethylene carbonate (EC) and carbon
(volume ratio of EC and DEC are 1 in the mixed solution of diethyl phthalate (DEC)：1) electrolyte, NaPF is made6A concentration of 1.0mol/
L is assembled into CR2032 button cells.
(2) assembling of lithium rechargeable battery：
The final product that embodiment is prepared is with acetylene black, binding agent PVDF according to 8:1:1 weight ratio mixing, adds in
Nmp solution grinds in the environment of air drying and forms slurry, then slurry is evenly applied on copper foil of affluxion body, dry
It is cut into the pole piece of a diameter of 1cm afterwards, under vacuum after 80 DEG C of dry 12h, it is spare to be transferred to glove box.Button cell is with gold
Category sodium is electrode, by NaPF6It is dissolved in the mixed solution of ethylene carbonate (EC) and diethyl carbonate (DEC) (EC and DEC's
Volume ratio is 1：1) electrolyte, NaPF is made6A concentration of 1.0mol/L is assembled into CR2032 button cells.
To the negative electrode active material of alkali metal secondary battery made from following embodiment and the secondary electricity of alkali metal assembled
Pond carries out testing respectively as follows：
(1) scanning electron microscope (SEM) test of granular precursor：Sample preparation procedure is：Dried powder is uniform
It applies on conducting resinl, gold-plated processing after metal spraying processing, is sent into the pattern sight that sample room carries out material with the electric conductivity of reinforcing material
It examines.Use field emission scanning electron microscope (FEI, Quanata 200f), accelerating potential 20KV.
(1) negative electrode active material Elemental redistribution：
The preparation process of sample is：Sample powder is taken, absolute ethyl alcohol is added in, sample suspension is obtained after ultrasonic disperse, with drop
Pipe takes suspension to drop to copper grid or carbon film, vacuumizes the dry sample room that is re-fed into and observes.Instrument model is HRTEM, Tecnai
G2 F20 S-TWIN, 200KV.
(2) negative electrode active material transmission electron microscope (TEM) is tested：
The preparation process of sample is：Sample powder is taken, absolute ethyl alcohol is added in, sample suspension is obtained after ultrasonic disperse, with drop
Pipe takes suspension to drop to copper grid or carbon film, vacuumizes the dry sample room that is re-fed into and observes.Instrument model is HRTEM, Tecnai
G2 F20 S-TWIN, 200KV.
(3) negative electrode active material X-ray diffraction (XRD) is tested：
The Crystal Structure of material uses X-ray diffractometer, model Rigaku Ultima IV-185 types, Co K α
For radioactive source,Pipe pressure is 40kV, Guan Liuwei 35mA.Test process is：Uniform powder sample pressure will be ground
System is in glass sample slot, being subsequently placed on X-ray diffractometer specimen holder and being tested, and scanning range is 10 °~90 °, scanning
Speed is 1.5~8 ° of min-1。
(4) negative electrode active material does sodium ion secondary battery cathode 20 weeks property charging and discharging curves before charge and discharge under 0.1C：
Constant current charge-discharge test is carried out using Land battery test systems, current density is 25mA g-1, voltage range
0.001-2.5V。
(5) negative electrode active material does the test of sodium ion secondary battery cathode high rate performance：
Constant current charge-discharge test is carried out using Land battery test systems, current density is 25mA g-1, 50mA g-1,
100mA g-1, 200mA g-1, 500mA g-1, 1A g-1, voltage range 0.001-2.5V.
(6) negative electrode active material does negative electrode of lithium ion battery 20 weeks property charging and discharging curves before charge and discharge under 0.1C：
Constant current charge-discharge test is carried out using Land battery test systems, current density is 50mA g-1, voltage range
0.001-2.5V。
(7) negative electrode active material does the test of lithium ion secondary battery negative pole high rate performance：
Constant current charge-discharge test is carried out using Land battery test systems, current density is 50mA g-1, 100mA g-1,
200mA g-1, 500mA g-1, 1A g-1, 2A g-1, 5A g-1, voltage range 0.001-2.5V.
Embodiment 1
The present embodiment be used for the preparation for illustrating the negative electrode active material of the present invention and its sodium ion secondary battery and lithium from
Application in sub- secondary cell, the specific steps are：
(1) the surfactant PVP-K30 for weighing 30mg is dissolved in 60ml ethylene glycol solvents, and magnetic agitation 360min is allowed to
Dissolving；Under magnetic agitation, the Fe (NO of 30mg are added in3)3·9H2O continues to stir 2h, obtains mixed solution 1；
(2) mixed solution 1 is transferred in three-necked flask and be put into oil bath pan, add condensate return, control mixing speed
For 600r/min, back flow reaction 90min, is transferred in reaction kettle after reaction at 90 DEG C, and sealing is reacted at 180 DEG C
12h, centrifugation, after precipitation is washed with ethyl alcohol, 60 DEG C of drying obtain granular precursor.
(3) isopropyl titanate for weighing 100mg is dissolved in 30ml ethyl alcohol, obtains mixed solution 2；
(4) 50mg granular precursors are dissolved in mixed solution 2,60 DEG C of stirrings are volatilized until ethyl alcohol, obtain intermediate product
1。
(5) intermediate product 1 is sintered 2h in air atmosphere at 450 DEG C, temperature rate is 2 DEG C/min, obtains whole production
Object, i.e., a kind of alkali metal secondary battery negative electrode active material.
SEM tests are carried out to granular precursor, the results are shown in Figure 1, and granular precursor uniformly disperses and pattern is uniform.
Elemental analysis is carried out to final product, Elemental redistribution is as shown in Fig. 2, nucleocapsid point is presented in element in final product
Cloth.Fe Elemental redistributions are as shown in figure 3, Fe elements are evenly distributed on sphere center position；Ti Elemental redistributions are as shown in figure 4, Ti elements are equal
It is even to be distributed in spherical structure outer layer；O Elemental redistributions are as shown in figure 5, O elements are evenly distributed in spherical structure.
TEM tests are carried out to final product, the results are shown in Figure 6, and final product has apparent nucleocapsid feature, and material
Grain size is 200-250nm, and nanometer titanium dioxide-coated layer thickness is 50-80nm.
XRD tests are carried out to final product, the results are shown in Figure 7, and iron and di-iron trioxide peak shape are apparent；At 30 °
Small peak proves the presence of titanium dioxide.
By elemental analysis, TEM tests and the XRD tests to final product, it is the spherical nucleocapsid coated entirely to show final product
Structure, shell are nano-titanium dioxide, and core is nanometer di-iron trioxide and Nanoscale Iron.
The sodium ion secondary battery of final product assembling is tested for the property, it is as a result as follows：
0.1C charging and discharging curves as shown in figure 8, its first all discharge capacity up to 385mAh g-1, first week coulombic efficiency is
83.92%.
High rate performance test result is as shown in figure 9, electric current is 1A g-1When discharge capacity reach 160mAh g-1, coulombic efficiency>
99%, it follows that when the negative electrode active material of the alkali metal secondary battery is as sodium ion secondary battery cathode, do not drawing
Good chemical property can be shown in the case of entering conductive carbon.
The lithium rechargeable battery of final product assembling is tested for the property：
0.1C charging and discharging curves are as shown in Figure 10, and first week discharge capacity is up to 1212.9mAh g-1, recycle 20 Zhou Hourong
It measures as 999.1mAh g-1。
High rate performance test result is as shown in figure 11, and electric current is 5A g-1When discharge capacity reach 201.6mAh g-1, coulomb effect
Rate>99%, and it can be seen that when electric current returns to low current, reversible capacity gos up.It follows that the alkali metal secondary battery
Negative electrode active material as lithium ion secondary battery negative pole when good electricity can be shown in the case where not introducing conductive carbon
Chemical property.
Comparative example 1
The present embodiment be used for illustrate not coat nano-titanium dioxide negative electrode active material preparation and its sodium from
Application in sub- secondary cell.
(1) the surfactant PVP-K30 for weighing 30mg is dissolved in 60ml ethylene glycol solvents, and magnetic agitation 360min is allowed to
Dissolving；
(2) under magnetic agitation, by the Fe (NO of 30mg3)3·9H2O is added in the solvent of step (1), persistently stirs 2h；
(3) solution of step (2) is transferred in three-necked flask and be put into oil bath pan, add condensate return, control stirring
Speed is 600r/min, and back flow reaction 90min, is transferred in reaction kettle after reaction at 90 DEG C, sealing, at 180 DEG C
12h is reacted, centrifugation, after being washed with ethyl alcohol, 60 DEG C of drying obtain granular precursor.
It will obtain granular precursor and be sintered 2h at 450 DEG C in air atmosphere, temperature rate is 2 DEG C/min, is heat-treated
After obtain final product.
The lithium rechargeable battery of final product assembling is tested for the property, as a result as shown in figure 12,0.1C charge and discharge electrical measurements
The lower first all charging capacitys of examination are 159.6mAh g-1, coulombic efficiency 33.35%.Discharge capacity is 86.1mAh after 70 weeks cycles
g-1。
It is found by being compared with embodiment 1, using a kind of alkali metal secondary battery negative electrode active material described in embodiment 1
The alkali metal secondary battery assembled shows high reversible capacity, high rate capability.
Invention include but not limited to above example, it is every carried out under the spirit and principles in the present invention it is any equivalent
Replacement or local improvement, all will be regarded as within protection scope of the present invention.
Claims (10)
1. a kind of alkali metal secondary battery negative electrode active material, it is characterised in that：The negative electrode active material is the ball coated entirely
Forming core shell structure, shell are nano-titanium dioxide, and core includes nanometer di-iron trioxide；The mass ratio of ferro element and titanium elements is 5-
15：1.
2. a kind of alkali metal secondary battery negative electrode active material as described in claim 1, it is characterised in that：The negative electrode active
The spherical particle size of material is 200-300nm.
3. a kind of alkali metal secondary battery negative electrode active material as described in claim 1, it is characterised in that：The nano-silica
It is impalpable structure or anatase structured to change titanium shell.
4. a kind of alkali metal secondary battery negative electrode active material as described in claim 1, it is characterised in that：The nano-silica
The thickness for changing titanium shell is 5-100nm.
5. a kind of alkali metal secondary battery negative electrode active material as described in claim 1, it is characterised in that：Core is three oxygen of nanometer
Change the mixture of two iron and nano iron particles, nano iron particles are distributed in the outermost layer of core.
6. a kind of preparation method of alkali metal secondary battery negative electrode active material as claimed in any one of claims 1 to 5, wherein,
It is characterized in that：The method step is as follows：
(1) surfactant is dissolved in ethylene glycol, surfactant concentration 0.1-2g/L, magnetic agitation 30-360min makes
Dissolving；Under magnetic agitation, molysite is added in, continues stirring to a period of time is completely dissolved, obtains mixed solution 1；
(2) back flow reaction 30-360min, mixing speed 200-1200r/min, reaction at 60-220 DEG C by mixed solution 1
After, the hydro-thermal reaction 6-24h at 120-180 DEG C, centrifugation, after precipitation is washed with ethyl alcohol, 60-80 DEG C of drying obtains forerunner
Body particle；
(3) titanium salt is dissolved in ethyl alcohol, the mass ratio of titanium salt and ethyl alcohol is 1:4-8 obtains mixed solution 2；
(4) granular precursor that step (2) obtains is dissolved in mixed solution 2, the mass ratio of granular precursor and mixed solution 2
For 3-10:1,60-120 DEG C of stirring is volatilized completely to ethyl alcohol, obtains intermediate product；
(5) intermediate product is sintered 1-6h at 300-600 DEG C, heating rate is 1-5 DEG C/min, and it is secondary to obtain a kind of alkali metal
The negative electrode active material of battery.
7. a kind of preparation method of alkali metal secondary battery negative electrode active material as claimed in claim 6, it is characterised in that：Institute
Surfactant is stated as polyvinylpyrrolidone-K30, cetyl trimethylammonium bromide or ethylenediamine tetra-acetic acid.
8. a kind of preparation method of alkali metal secondary battery negative electrode active material as claimed in claim 6, it is characterised in that：Institute
Molysite is stated as Fe (NO3)3·9H2O or FeCl3；The titanium salt is isopropyl titanate, butyl titanate or titanium tetrachloride.
9. a kind of sodium ion secondary battery, it is characterised in that：The negative electrode active material of the battery is arbitrary for Claims 1 to 5
A kind of negative electrode active material of alkali metal secondary battery described in one.
10. a kind of lithium rechargeable battery, it is characterised in that：The negative electrode active material of the battery is arbitrary for Claims 1 to 5
A kind of negative electrode active material of alkali metal secondary battery described in one.
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