CN107017403A - A kind of cell negative electrode material and preparation method thereof and its application - Google Patents
A kind of cell negative electrode material and preparation method thereof and its application Download PDFInfo
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- CN107017403A CN107017403A CN201710421964.7A CN201710421964A CN107017403A CN 107017403 A CN107017403 A CN 107017403A CN 201710421964 A CN201710421964 A CN 201710421964A CN 107017403 A CN107017403 A CN 107017403A
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Abstract
The invention belongs to cell art, more particularly to a kind of cell negative electrode material, the negative material has core shell structure, and wherein nuclear structure is SnSexS1‑x, wherein, 0 ＜ x ＜ 1, shell structure is carbon.Relative to prior art, SnSexS1‑xWith good chemical property, such as, it stores up lithium excellent performance, but its Volume Changes in cyclic process is larger, and big Volume Changes can cause the efflorescence of electrode material, burst apart and fail, and cause cycle performance to be deteriorated, and carbon coating then can be to SnSexS1‑xEnter row constraint, reduce its Volume Changes, improve its cycle performance so that SnSexS1‑xLithium ion battery and sodium-ion battery can be applied.In addition, the invention also discloses the preparation method of the negative material and its application.
Description
Technical field
The invention belongs to cell art, more particularly to a kind of cell negative electrode material and preparation method thereof and its application,
The battery includes lithium ion battery and sodium-ion battery.
Background technology
Lithium ion battery is widely used on electronic product and power vehicle at present, and sodium-ion battery is mainly used in greatly
Type energy storage.Due to two kinds of respective advantages of battery：Lithium ion battery efficiency for charge-discharge is high, and energy density is high, sodium-ion battery money
Source is enriched, with low cost.Currently commercially purposes most wide lithium ion battery negative material surely belongs to graphite, but graphite cathode by
It is relatively low in its charging/discharging voltage platform, the defects such as Li dendrite can be produced and barrier film is pierced through so that bringing safety problem, Er Qieshi
Ink is because interlamellar spacing is small and can not be applied to the negative pole of sodium-ion battery, and the positive exploitation of current researchers is new to be born
Pole material substitutes graphite cathode, and it is desirable that negative material can be applied in lithium ion battery and sodium-ion battery simultaneously.
In view of this, the present invention is intended to provide a kind of cell negative electrode material and preparation method thereof, the negative material can be same
When be applied in lithium ion battery and sodium-ion battery.
The content of the invention
An object of the present invention is：In view of the shortcomings of the prior art, a kind of cell negative electrode material is provided, the negative pole
Material can be applied in lithium ion battery and sodium-ion battery simultaneously.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
A kind of cell negative electrode material, the negative material has core shell structure, and wherein nuclear structure is SnSexS1-x, wherein, 0
＜ x ＜ 1, shell structure is carbon.
Improved as one kind of cell negative electrode material of the present invention, the nuclear structure is SnSe0.5S0.5。
Improved as one kind of cell negative electrode material of the present invention, the mass ratio of the shell structure and the nuclear structure is 1：
(3-10), the thickness of the shell structure is 100nm-10 μm.
Relative to prior art, SnSexS1-xWith good chemical property, such as, it stores up lithium excellent performance, still
Its Volume Changes in cyclic process is larger, and big Volume Changes can cause the efflorescence of electrode material, burst apart and fail, and cause to follow
Ring degradation, carbon coating then can be to SnSexS1-xEnter row constraint, reduce its Volume Changes, improve its cycle performance so that
SnSexS1-xLithium ion battery and sodium-ion battery can be applied.In a word, the negative material can be used for simultaneously lithium ion battery and
Sodium-ion battery, with high specific capacity, excellent cycle performance and high rate performance.
It is another object of the present invention to provide a kind of preparation method of cell negative electrode material of the present invention, at least
Comprise the following steps：
1) synthesis of presoma：
In the environment of 80 DEG C -120 DEG C, S powder and Se powder are dissolved in the three mouth flasks equipped with diethylene glycol (DEG) (DEG) simultaneously
It is stirred vigorously, then passes to inert gas, remove the air in flask, ethylenediamine (EN) is instilled in above-mentioned solution, is transferred to
In 130 DEG C -150 DEG C of environment, continue to stir, and add SnCl4·5H2O, is again heated to 190 DEG C -220 DEG C, is incubated 1h-5h
Afterwards, it is cooled to room temperature；Cleaned and centrifuged with ethanol again, be dried to obtain brownish-yellow powder；
2) synthesis of nuclear structure：
By step 1) in precursor under inert gas shielding atmosphere, in sintering 15h-30h at 300 DEG C -500 DEG C, so
Cooling obtains black powder afterwards；
3) synthesis of cell negative electrode material：
By step 2) obtained black powder added in the carbon source aqueous solution, and ultrasonic mixing is uniform, is then transferred to hydro-thermal anti-
Answer in kettle, 1h-5h is kept in the environment of 160 DEG C -200 DEG C, then furnace cooling carries out suction filtration, then at 400 DEG C -700 DEG C
2h-6h is sintered in the batch-type furnace of inert gas shielding, then furnace cooling, finally obtain black powder.
Be used as a kind of improvement of the preparation method of cell negative electrode material of the present invention, step 1), step 2) and step 3) in
Inert gas is nitrogen or argon gas.
It is used as a kind of improvement of the preparation method of cell negative electrode material of the present invention, step 1) in, S powder and Se powder rub
Your ratio is x：(1-x), wherein, 0 ＜ x ＜ 1.
Improved as a kind of the of preparation method of cell negative electrode material of the present invention, the carbon source is glucose, citric acid, hard
At least one of resin acid and sucrose.
Improved as a kind of the of preparation method of cell negative electrode material of the present invention, step 1) in, diethylene glycol (DEG) (DEG) and second two
The volume ratio of amine (EN) is (20-25):1.
Improved as a kind of the of preparation method of cell negative electrode material of the present invention, S powder and Se powder are adding three mouths burning
It is first well mixed with mortar before bottle.
Relative to prior art, the present invention is first using polyalcohol --- and diethylene glycol (DEG) (DEG) auxiliary law prepares presoma,
In the reaction system of diethylene glycol (DEG) (DEG) and additive ethylenediamine, SnSexS1-xNucleation quickly because, diethylene glycol (DEG) is used as band
There is the excellent block agent of multiple hydroxyl groups, " can tightly capture " free Sn in solution2+Ion, with S2-With
Se2-The addition of ion, S2-And Se2-Ion is promptly attracted to Sn2+Near ion, the amorphous of grey black is formed
SnSexS1-xColloid, moreover, ethylenediamine can be in the form of bidentate ligand and Sn2+Ion forms metastable Sn (en)2Complexing
Thing, SnSexS1-xAfter colloid nucleation, due to the steric effect of ethylenediamine, SnS and SnSe particles will the life of formability zero dimension
Long growth unit, after oversintering, just can form SnSexS1-x, this method can be very good control SnSexS1-xParticle diameter
And pattern, make it have good chemical property.Then one layer of carbon-coating is uniformly coated on its surface by hydro-thermal method again, greatly
Its circulation expansion is reduced greatly, improves its cycle performance.In a word, the tin selenium sulphur compound obtained using the method for the present invention can be simultaneously
For lithium ion battery and sodium-ion battery negative pole, with high specific capacity, excellent cycle performance and high rate performance.
Present invention further teaches one kind using cell negative electrode material of the present invention in lithium ion battery and sodium ion electricity
Application in pond.Practice have shown that：The negative material is applied in lithium ion battery, and charging/discharging voltage is interval in 0.01~3.0V,
The negative material is applied in sodium-ion battery, and charging/discharging voltage interval is in 0.01~3.0V.The electric discharge specific volume of the negative material
Amount is higher, and specific discharge capacity conservation rate is higher after the circle of circulation 500.
Brief description of the drawings
Fig. 1 is the XRD of the negative material prepared in the present invention using the method in embodiment 1.
The SEM of negative materials of the Fig. 2 to be prepared in the present invention using the method in embodiment 1 is schemed, including (a) and (b) two
Figure.
Fig. 3 for the present invention in use embodiment 1 in method prepare negative material be used in lithium ion battery in when not
With the charging and discharging curve under multiplying power.
Fig. 4 for the present invention in use embodiment 1 in method prepare negative material be used in lithium ion battery in when
The long circulating performance curve of lithium ion battery under 0.5A/g current densities.
Fig. 5 for the present invention in use embodiment 1 in method prepare negative material be used in sodium-ion battery in when not
With the charging and discharging curve under multiplying power.
Fig. 6 for the present invention in use embodiment 1 in method prepare negative material be used in sodium-ion battery in when
The long circulating performance curve of lithium ion battery under 0.2A/g current densities.
Embodiment
Illustrate technical scheme, but protection scope of the present invention not limited to this with specific embodiment below.
Embodiment 1
A kind of cell negative electrode material is present embodiments provided, the negative material has core shell structure, wherein nuclear structure is
SnSe0.5S0.5, shell structure is carbon.The mass ratio of shell structure and nuclear structure is 1：5, the thickness of shell structure is 100nm-10 μm.
The preparation method of the cell negative electrode material at least comprises the following steps：
1) synthesis of presoma：
0.01mol S powder and 0.01mol Se powder are well mixed with mortar, in the environment of 100 DEG C, by S powder
Dissolve in the three mouth flasks equipped with 45mL diethylene glycol (DEG)s (DEG) and be stirred vigorously with Se powder, then pass to 10 minutes nitrogen, remove
Air in flask, 2mL ethylenediamines (EN) are instilled in above-mentioned solution, are transferred to 140 DEG C of environment, continue to stir, and add
0.01mol SnCl4·5H2O, is heated to 200 DEG C, after being incubated 2 hours, then room temperature cooling.Cleaned with ethanol and centrifuge 4 times, most
Afterwards brownish-yellow powder is dried to obtain in 80 DEG C of drying box.
2) synthesis of nuclear structure：
By step 1) in precursor sintered 20 hours in the batch-type furnace that 400 DEG C of argon gas are protected, then furnace cooling, most
After obtain black powder.
3) synthesis of cell negative electrode material：
By 0.3g steps 1) in black powder add 0.5M D/W in, ultrasound 30 minutes, then shift
Into hydrothermal reaction kettle, kept for 3 hours in the environment of 180 DEG C, furnace cooling, then carry out suction filtration, then protect in 500 DEG C of argon gas
Sintered 4 hours in the batch-type furnace of shield, then furnace cooling finally obtains black powder.
The XRD of the negative material is as shown in figure 1, as seen from Figure 1：The XRD peak shape of the negative material is sharp, table
The crystallinity of the bright material is preferable, and its each peak energy enough belongs to 48-1225 cards (SnSe0.5S0.5/C)。
The SEM figures of the negative material are as shown such as (a) and (b) in Fig. 2, as seen from Figure 2, and it has more spherical
Structure.
The negative material is applied in lithium ion battery, charging/discharging voltage interval is in 0.01~3.0V.Wherein, lithium ion
The positive active material of battery is cobalt acid lithium, and the solute of electrolyte is 1mol/L LiFP6, the solvent of electrolyte for DMC, DEC and
PC mixed solvent, the volume ratio of three is 1:1:1, barrier film is PP.The negative material in 0.1A/g, 0.2A/g, 0.5A/g,
Specific discharge capacity under 0.8A/g, 1.0A/g, 2.0A/g, 5.0A/g current density is 989mAh/g, 830mAh/g,
729mAh/g, 673mAh/g, 646mAh/g, the result 553mAh/g, 389mAh/g as shown in Figure 3, in 0.5A/
Specific discharge capacity is maintained at 814mAh/g after the circle of circulation 500 under g current density, and the result is as shown in Figure 4.
The negative material is applied in sodium-ion battery, and charging/discharging voltage interval is in 0.01~3.0V.Wherein, sodium ion electricity
The positive active material in pond is phosphoric acid ferrisodium, and the solute of electrolyte is 1mol/L NaFP6, the solvent of electrolyte for DMC, DEC and
PC mixed solvent, the volume ratio of three is 1:1:1, barrier film is PP.The negative material in 0.1A/g, 0.2A/g, 0.5A/g,
Under 0.8A/g, 1A/g current density, specific discharge capacity is respectively 683mAh/g, 612mAh/g, 549mAh/g,
525mAh/g, 506mAh/g, the result are as shown in Figure 5.Specific capacity is maintained at after the circle of circulation 100 under 0.2A/g multiplying powers
430mAh/g, the result is as shown in Figure 6.
Embodiment 2
A kind of cell negative electrode material is present embodiments provided, negative material has core shell structure, and wherein nuclear structure is
SnSe1/3S2/3, shell structure is carbon.Wherein.The mass ratio of shell structure and nuclear structure is 1：7, the thickness of shell structure is 100nm-
10μm。
The preparation method of the cell negative electrode material at least comprises the following steps：
1) synthesis of presoma：
0.03mol S powder and 0.015mol Se powder are well mixed with mortar, in the environment of 110 DEG C, by S powder
End and Se powder dissolve in the three mouth flasks equipped with 47mL diethylene glycol (DEG)s (DEG) and are stirred vigorously, and then pass to 10 minutes nitrogen, remove
The air gone in flask, 2mL ethylenediamines (EN) are instilled in above-mentioned solution, are transferred to 145 DEG C of environment, continue to stir, and add
Enter 0.01mol SnCl4·5H2O, is heated to 210 DEG C, after being incubated 3 hours, then room temperature cooling.Cleaned and centrifuged 4 times with ethanol,
Finally brownish-yellow powder is dried to obtain in 85 DEG C of drying box.
2) synthesis of nuclear structure：
By step 1) in precursor sintered 22 hours in the batch-type furnace that 450 DEG C of argon gas are protected, then furnace cooling, most
After obtain black powder.
3) synthesis of cell negative electrode material：
By 0.5g steps 1) in black powder add 0.5M aqueous sucrose solution in, ultrasound 30 minutes, be then transferred to
In hydrothermal reaction kettle, kept for 3.5 hours in the environment of 205 DEG C, furnace cooling, then carry out suction filtration, then protect in 600 DEG C of argon gas
Sintered 5 hours in the batch-type furnace of shield, then furnace cooling finally obtains black powder.
The negative material is applied in lithium ion battery, charging/discharging voltage interval is in 0.01~3.0V.Wherein, lithium ion
The positive active material of battery is cobalt acid lithium, and the solute of electrolyte is 1mol/L LiFP6, the solvent of electrolyte for DMC, DEC and
PC mixed solvent, the volume ratio of three is 1:1:1, barrier film is PP.The negative material in 0.1A/g, 0.2A/g, 0.5A/g,
Specific discharge capacity under 0.8A/g, 1.0A/g, 2.0A/g, 5.0A/g current density is 995mAh/g, 833mAh/g,
726mAh/g, 671mAh/g, 649mAh/g, 559mAh/g, 383mAh/g, are followed under 0.2A/g current density
Specific discharge capacity is maintained at 817mAh/g after ring 500 is enclosed.
The negative material is applied in sodium-ion battery, and charging/discharging voltage interval is in 0.01~3.0V.Wherein, sodium ion electricity
The positive active material in pond is phosphoric acid ferrisodium, and the solute of electrolyte is 1mol/L NaFP6, the solvent of electrolyte for DMC, DEC and
PC mixed solvent, the volume ratio of three is 1:1:1, barrier film is PP.The negative material in 0.1A/g, 0.2A/g, 0.5A/g,
Under 0.8A/g, 1A/g current density, specific discharge capacity is respectively 688mAh/g, 610mAh/g, 546mAh/g,
522mA·h/g,509mA·h/g.Specific capacity is maintained at 431mAh/g after the circle of circulation 100 under 0.2A/g multiplying powers.
Embodiment 3
A kind of cell negative electrode material is present embodiments provided, the negative material has core shell structure, wherein nuclear structure is
SnSe0.2S0.8, shell structure is carbon.The mass ratio of shell structure and nuclear structure is 1：5, the thickness of shell structure is 100nm-10 μm.
The preparation method of the cell negative electrode material at least comprises the following steps：
1) synthesis of presoma：
0.04mol S powder and 0.01mol Se powder are well mixed with mortar, in the environment of 95 DEG C, by S powder
Dissolve in the three mouth flasks equipped with 40mL diethylene glycol (DEG)s (DEG) and be stirred vigorously with Se powder, then pass to 10 minutes nitrogen, remove
Air in flask, 2mL ethylenediamines (EN) are instilled in above-mentioned solution, are transferred to 150 DEG C of environment, continue to stir, and add
0.01mol SnCl4·5H2O, is heated to 205 DEG C, after being incubated 4 hours, then room temperature cooling.Cleaned with ethanol and centrifuge 4 times, most
Afterwards brownish-yellow powder is dried to obtain in 85 DEG C of drying box.
2) synthesis of nuclear structure：
By step 1) in precursor sintered 28 hours in the batch-type furnace that 350 DEG C of argon gas are protected, then furnace cooling, most
After obtain black powder.
3) synthesis of cell negative electrode material：
By 0.5g steps 1) in black powder add 0.5M aqueous citric acid solution in, ultrasound 30 minutes, then shift
Into hydrothermal reaction kettle, kept for 4 hours in the environment of 175 DEG C, furnace cooling, then carry out suction filtration, then protect in 450 DEG C of argon gas
Sintered 5 hours in the batch-type furnace of shield, then furnace cooling finally obtains black powder.
The negative material is applied in lithium ion battery, charging/discharging voltage interval is in 0.01~3.0V.Wherein, lithium ion
The positive active material of battery is cobalt acid lithium, and the solute of electrolyte is 1mol/L LiFP6, the solvent of electrolyte for DMC, DEC and
PC mixed solvent, the volume ratio of three is 1:1:1, barrier film is PP.The negative material in 0.1A/g, 0.2A/g, 0.5A/g,
Specific discharge capacity under 0.8A/g, 1.0A/g, 2.0A/g, 5.0A/g current density is 995mAh/g, 827mAh/g,
741mAh/g, 689mAh/g, 630mAh/g, 567mAh/g, 378mAh/g, are followed under 0.2A/g current density
Specific discharge capacity is maintained at 817mAh/g after ring 500 is enclosed.
The negative material is applied in sodium-ion battery, and charging/discharging voltage interval is in 0.01~3.0V.Wherein, sodium ion electricity
The positive active material in pond is phosphoric acid ferrisodium, and the solute of electrolyte is 1mol/L NaFP6, the solvent of electrolyte for DMC, DEC and
PC mixed solvent, the volume ratio of three is 1:1:1, barrier film is PP.The negative material in 0.1A/g, 0.2A/g, 0.5A/g,
Under 0.8A/g, 1A/g current density, specific discharge capacity is respectively 691mAh/g, 622mAh/g, 544mAh/g,
521mA·h/g,513mA·h/g.Specific capacity is maintained at 428mAh/g after the circle of circulation 100 under 0.2A/g multiplying powers.
Embodiment 4
A kind of cell negative electrode material is present embodiments provided, the negative material has core shell structure, wherein nuclear structure is
SnSe0.75S0.25, shell structure is carbon.The mass ratio of shell structure and nuclear structure is 1：9, the thickness of shell structure is 100nm-10 μm.
The preparation method of the cell negative electrode material at least comprises the following steps：
1) synthesis of presoma：
0.01mol S powder and 0.03mol Se powder are well mixed with mortar, in the environment of 90 DEG C, by S powder
Dissolve in the three mouth flasks equipped with 43mL diethylene glycol (DEG)s (DEG) and be stirred vigorously with Se powder, then pass to 10 minutes nitrogen, remove
Air in flask, 2mL ethylenediamines (EN) are instilled in above-mentioned solution, are transferred to 135 DEG C of environment, continue to stir, and add
0.01mol SnCl4·5H2O, is heated to 190 DEG C, after being incubated 2.5 hours, then room temperature cooling.Cleaned and centrifuged 4 times with ethanol,
Finally brownish-yellow powder is dried to obtain in 90 DEG C of drying box.
2) synthesis of nuclear structure：
By step 1) in precursor sintered 30 hours in the batch-type furnace that 350 DEG C of argon gas are protected, then furnace cooling, most
After obtain black powder.
3) synthesis of cell negative electrode material：
By 0.3g steps 1) in black powder add 0.5M D/W in, ultrasound 30 minutes, then shift
Into hydrothermal reaction kettle, kept for 3 hours in the environment of 180 DEG C, furnace cooling, then carry out suction filtration, then protect in 550 DEG C of argon gas
Sintered 3.5 hours in the batch-type furnace of shield, then furnace cooling finally obtains black powder.
The negative material is applied in lithium ion battery, charging/discharging voltage interval is in 0.01~3.0V.Wherein, lithium ion
The positive active material of battery is cobalt acid lithium, and the solute of electrolyte is 1mol/L LiFP6, the solvent of electrolyte for DMC, DEC and
PC mixed solvent, the volume ratio of three is 1:1:1, barrier film is PP.The negative material in 0.1A/g, 0.2A/g, 0.5A/g,
Specific discharge capacity under 0.8A/g, 1.0A/g, 2.0A/g, 5.0A/g current density is 980mAh/g, 820mAh/g,
722mAh/g, 671mAh/g, 641mAh/g, 542mAh/g, 378mAh/g, are followed under 0.2A/g current density
Specific discharge capacity is maintained at 801mAh/g after ring 500 is enclosed.
The negative material is applied in sodium-ion battery, and charging/discharging voltage interval is in 0.01~3.0V.Wherein, sodium ion electricity
The positive active material in pond is phosphoric acid ferrisodium, and the solute of electrolyte is 1mol/L NaFP6, the solvent of electrolyte for DMC, DEC and
PC mixed solvent, the volume ratio of three is 1:1:1, barrier film is PP.The negative material in 0.1A/g, 0.2A/g, 0.5A/g,
Under 0.8A/g, 1A/g current density, specific discharge capacity is respectively 675mAh/g, 603mAh/g, 541mAh/g,
520mA·h/g,502mA·h/g.Specific capacity is maintained at 422mAh/g after the circle of circulation 100 under 0.2A/g multiplying powers.
Embodiment 5
A kind of cell negative electrode material is present embodiments provided, the negative material has core shell structure, wherein nuclear structure is
SnSe0.1S0.9, shell structure is carbon.The mass ratio of shell structure and nuclear structure is 1：9, the thickness of shell structure is 100nm-10 μm.
The preparation method of the cell negative electrode material at least comprises the following steps：
1) synthesis of presoma：
0.09mol S powder and 0.01mol Se powder are well mixed with mortar, in the environment of 110 DEG C, by S powder
Dissolve in the three mouth flasks equipped with 48mL diethylene glycol (DEG)s (DEG) and be stirred vigorously with Se powder, then pass to 10 minutes nitrogen, remove
Air in flask, 2mL ethylenediamines (EN) are instilled in above-mentioned solution, are transferred to 130 DEG C of environment, continue to stir, and add
0.01mol SnCl4·5H2O, is heated to 210 DEG C, after being incubated 2.5 hours, then room temperature cooling.Cleaned and centrifuged 4 times with ethanol,
Finally brownish-yellow powder is dried to obtain in 80 DEG C of drying box.
2) synthesis of nuclear structure：
By step 1) in precursor sintered 24 hours in the batch-type furnace that 450 DEG C of argon gas are protected, then furnace cooling, most
After obtain black powder.
3) synthesis of cell negative electrode material：
By 0.3g steps 1) in black powder add 0.5M stearic aqueous acid in, ultrasound 30 minutes, then shift
Into hydrothermal reaction kettle, kept for 3 hours in the environment of 190 DEG C, furnace cooling, then carry out suction filtration, then protect in 600 DEG C of argon gas
Sintered 3 hours in the batch-type furnace of shield, then furnace cooling finally obtains black powder.
The negative material is applied in lithium ion battery, charging/discharging voltage interval is in 0.01~3.0V.Wherein, lithium ion
The positive active material of battery is cobalt acid lithium, and the solute of electrolyte is 1mol/L LiFP6, the solvent of electrolyte for DMC, DEC and
PC mixed solvent, the volume ratio of three is 1:1:1, barrier film is PP.The negative material in 0.1A/g, 0.2A/g, 0.5A/g,
Specific discharge capacity under 0.8A/g, 1.0A/g, 2.0A/g, 5.0A/g current density is 995mAh/g, 842mAh/g,
738mAh/g, 682mAh/g, 651mAh/g, 561mAh/g, 397mAh/g, are followed under 0.2A/g current density
Specific discharge capacity is maintained at 820mAh/g after ring 500 is enclosed.
The negative material is applied in sodium-ion battery, and charging/discharging voltage interval is in 0.01~3.0V.Wherein, sodium ion electricity
The positive active material in pond is phosphoric acid ferrisodium, and the solute of electrolyte is 1mol/L NaFP6, the solvent of electrolyte for DMC, DEC and
PC mixed solvent, the volume ratio of three is 1:1:1, barrier film is PP.The negative material in 0.1A/g, 0.2A/g, 0.5A/g,
Under 0.8A/g, 1A/g current density, specific discharge capacity is respectively 692mAh/g, 621mAh/g, 561mAh/g,
532mA·h/g,511mA·h/g.Specific capacity is maintained at 441mAh/g after the circle of circulation 100 under 0.2A/g multiplying powers.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, the invention is not limited in embodiment disclosed and described above, to the present invention's
Some modifications and changes should also be as falling into the scope of the claims of the present invention.Although in addition, being used in this specification
Some specific terms, but these terms are merely for convenience of description, do not constitute any limitation to the present invention.
Claims (10)
1. a kind of cell negative electrode material, it is characterised in that：The negative material has core shell structure, and wherein nuclear structure is
SnSexS1-x, wherein, 0 ＜ x ＜ 1, shell structure is carbon.
2. cell negative electrode material according to claim 1, it is characterised in that the nuclear structure is SnSe0.5S0.5。
3. cell negative electrode material according to claim 1, it is characterised in that：The quality of the shell structure and the nuclear structure
Ratio is 1：(3-10), the thickness of the shell structure is 100nm-10 μm.
4. the preparation method of the cell negative electrode material described in a kind of claim 1, it is characterised in that at least comprise the following steps：
1) synthesis of presoma：
In the environment of 80 DEG C -120 DEG C, S powder and Se powder are dissolved in the three mouth flasks equipped with diethylene glycol (DEG) (DEG) and violent
Stirring, then passes to inert gas, removes the air in flask, and ethylenediamine (EN) is instilled in above-mentioned solution, 130 are transferred to
In DEG C -150 DEG C of environment, continue to stir, and add SnCl4·5H2O, is again heated to after 190 DEG C -220 DEG C, insulation 1h-5h, cold
But to room temperature；Cleaned and centrifuged with ethanol again, be dried to obtain brownish-yellow powder；
2) synthesis of nuclear structure：
By step 1) in precursor under inert gas shielding atmosphere, in sintering 15h-30h at 300 DEG C -500 DEG C, Ran Houleng
But black powder is obtained；
3) synthesis of cell negative electrode material：
By step 2) obtained black powder added in the carbon source aqueous solution, and ultrasonic mixing is uniform, is then transferred to hydrothermal reaction kettle
In, keep 1h-5h in the environment of 160 DEG C -200 DEG C, then furnace cooling carries out suction filtration, then in 400 DEG C -700 DEG C of inertia
2h-6h is sintered in the batch-type furnace of gas shield, then furnace cooling, finally obtain black powder.
5. the preparation method of cell negative electrode material according to claim 4, it is characterised in that step 1), step 2) and step
It is rapid 3) in inert gas be nitrogen or argon gas.
6. the preparation method of cell negative electrode material according to claim 4, it is characterised in that step 1) in, S powder and Se
The molar ratio of powder is x：(1-x), wherein, 0 ＜ x ＜ 1.
7. the preparation method of cell negative electrode material according to claim 4, it is characterised in that the carbon source be glucose,
At least one of citric acid, stearic acid and sucrose.
8. the preparation method of cell negative electrode material according to claim 4, it is characterised in that step 1) in, diethylene glycol (DEG)
(DEG) and ethylenediamine (EN) volume ratio be (20-25):1.
9. the preparation method of cell negative electrode material according to claim 4, it is characterised in that step 1) in, S powder and Se
Powder is first well mixed with mortar before three mouth flasks are added.
10. a kind of application of the cell negative electrode material described in claim 1 in lithium ion battery and sodium-ion battery.
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| CN113394396A (en) * | 2021-06-11 | 2021-09-14 | 重庆大学 | Bifunctional material SnSe1-xSx and preparation method thereof |
| CN113611831A (en) * | 2021-07-28 | 2021-11-05 | 西安航空学院 | MXene/SnSe0.5S0.5Composite material and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113005328A (en) * | 2021-02-23 | 2021-06-22 | 西安航空学院 | Tin-selenium-sulfur ternary alloy cathode material for sodium ion battery and preparation method and application thereof |
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| CN113394396A (en) * | 2021-06-11 | 2021-09-14 | 重庆大学 | Bifunctional material SnSe1-xSx and preparation method thereof |
| CN113394396B (en) * | 2021-06-11 | 2022-11-11 | 重庆大学 | Bifunctional material SnSe1-xSx and preparation method thereof |
| CN113611831A (en) * | 2021-07-28 | 2021-11-05 | 西安航空学院 | MXene/SnSe0.5S0.5Composite material and preparation method and application thereof |
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