CN106684327A - Negative electrode material of sodium ion battery and preparation method for negative electrode material - Google Patents
Negative electrode material of sodium ion battery and preparation method for negative electrode material Download PDFInfo
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- CN106684327A CN106684327A CN201610561754.3A CN201610561754A CN106684327A CN 106684327 A CN106684327 A CN 106684327A CN 201610561754 A CN201610561754 A CN 201610561754A CN 106684327 A CN106684327 A CN 106684327A
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- ion battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a negative electrode material of a sodium ion battery and a preparation method for the negative electrode material, and belongs to the field of battery material synthesis. The existing negative electrode material of the sodium ion battery has various kinds of problems and is not suitable for industrial application. The negative electrode material of the sodium ion battery is prepared from a metal elementary substance and a sulfur group elementary substance in a high temperature vacuum or inert gas through solid phase sintering, wherein the usage amount of the metal elementary substance is 14-80% based on molar ratio; and the sulfur group elementary substance is a sulfur elementary substance, a selenium elementary substance and/or a tellurium elementary substance. The negative electrode material of the sodium ion battery and the preparation method for the negative electrode material have the advantages of simple production process, simple operation, low production cost, low environmental pollution, high crystallinity, high yield and the like; and the electrode material prepared from the negative electrode material of the sodium ion battery and by the preparation method disclosed by the invention represents high cycling and rate capability, and has relatively high capacity retention ratio compared with the existing data.
Description
Technical field
The invention belongs to battery material synthesis field, more particularly to a kind of anode material of lithium-ion battery and its preparation side
Method.
Background technology
Lithium ion battery is widely applied as efficient energy storage device in portable electronic market, and to electronic
The extensive energy storage system extension of automobile, intelligent grid and regenerative resource.From the point of view of the application demand of extensive energy storage, preferably
Secondary cell is in addition to suitable chemical property, it is necessary to take into account society's Jing performance indicators such as aboundresources, price be cheap.
It is with low cost because sodium and lithium have similar physico-chemical property, and sodium aboundresources, it is the cell body for having very much development potentiality
System.With the continuous rising of the lithium ion battery prices of raw materials, for effective reduces cost, research sodium ion electricity has been started
The upsurge in pond.Sodium-ion battery is the new battery that the research worker of Centre National de la Recherche Scientifique are developed, by means of sodium from
Son shifts (rather than lithium ion) to store and discharge electric energy.But at present the sodium ion battery electrode material of most critical is still not
Commercially viable degree can be reached.
Sode cell negative material common at present mainly has carbon negative pole material, alloy material of cathode, metal chalcogenide compound
Negative material, metal phosphorus family compound negative material and the class of titanate negative material five.Carbon negative pole material mainly has：1st, graphite-like
Negative material, modified graphite, Graphene etc. belong to such, are characterized in wide material sources, cheap, prepare it is simple, circulation and
High rate performance is preferable, but first efficiency and theoretical capacity are relatively low；2nd, non-graphite negative material, various soft carbons and hard carbon belong to this
Class, is characterized in raw material sources extensively, and preparation process is simple, and interlamellar spacing and the degree of disorder are larger, and platform is relatively low, but theoretical capacity compared with
Low, circulation and high rate performance are poor.Alloy material of cathode mainly has：1st, tin negative pole material, is characterized in raw material sources extensively, reason
High by capacity, first efficiency is higher, but change in volume is big in charge and discharge process, and circulation and high rate performance are poor；2nd, antimony negative pole material
Material, is characterized in that theoretical capacity is high, but expensive raw material price, and change in volume is big in charge and discharge process, circulation and high rate performance compared with
Difference；3rd, phosphorus negative material, is characterized in raw material sources extensively, and theoretical capacity is high, but toxicity larger (white phosphorus), and poorly conductive is followed
Ring and high rate performance are poor.Metal chalcogenide compound negative material mainly has：1st, metal-oxide, Sb2O4、Fe2O3、SnO2、
MoO3、TiO2, Co3O4, CuO etc. belongs to such, is characterized in that theoretical capacity is high, but change in volume is big in charge and discharge process, structure
Unstable, electric conductivity is poor, and circulation and high rate performance are poor；2nd, metal sulfide, FeS2, FeS, MoS2, SnS2, SnS, CoS,
CuS, WS2Etc. belonging to such, it is characterized in that theoretical capacity is high, but change in volume is big in charge and discharge process, structural instability, circulation
Less stable；3rd, metal selenide, is characterized in electric conductivity preferably, and theoretical capacity is high, and high rate performance is preferable, but discharge and recharge
Change in volume is big in journey, and cycle performance is poor.Metal phosphorus family compound negative material mainly has：1st, ferro-phosphorus, FeP etc. belong to
In such, raw material sources are characterized in extensively, theoretical capacity is higher, but electric conductivity is poor, and circulation and high rate performance are poor；2nd, stannum
Phosphorus compound, Sn4P3Etc. belonging to such, it is characterized in cheap, theoretical capacity is high, but electric conductivity is poor, and volumetric expansion is tight
Weight, circulation and high rate performance are poor.Titanate negative material mainly has：Na2Ti3O7And Li4Ti5O12, it is characterized in that price is low
Honest and clean, Stability Analysis of Structures, change in volume is little, good cycle, but theoretical capacity is relatively low.
The commercialization of anode material of lithium-ion battery need to meet it is high performance simultaneously, minimize cost, simplify production
Technique.The a part of performance of negative material developed at present is relatively low, is not suitable for commercial application；Although another part performance reaches
It is possible to application, but material preparation process is complex, and very high to equipment requirements, input cost is big, wayward, it is difficult to realize
Produce in enormous quantities and apply, such as nano composite material, carbon composite etc.；And other process is simple, it is easy to control, and can
The anode material of lithium-ion battery compatible with existing lithium ion battery electrode material production technology, then capacity is relatively low and circulates steady
It is qualitative very poor, therefore also it is difficult to application.Therefore, exploitation synthesis technique is simple, equipment requirements are low, function admirable sodium ion
Cell negative electrode material, is remarkably contributing to realize the rapid popularization of sodium-ion battery and application, market potential is very huge.
The content of the invention
For the problem in the presence of prior art, it is an object of the invention to provide a kind of high performance sodium-ion battery
Negative material and preparation method thereof, the method process is simple, the requirement to production equipment is low, is the popularization and application of sodium-ion battery
There is provided a class can industrialization anode material of lithium-ion battery.
Another object of the present invention is to provide a kind of new high performance sodium-ion battery negative pole and sodium-ion battery.
For achieving the above object, the present invention is employed the following technical solutions：
A kind of anode material of lithium-ion battery, is characterized in that：Described negative material is existed by metal simple-substance and sulfur family simple substance
Solid-phase sintering is formed under conditions of high-temperature vacuum or noble gases, wherein, the consumption of described metal simple-substance is 14%~80%
Molar ratio, described sulfur family simple substance is sulphur simple substance, selenium simple substance and/or tellurium simple substance.
Further, the consumption of described metal simple-substance is 25%~50% molar ratio.
Further, the consumption of described metal simple-substance is 33% molar ratio.
Further, described metal simple-substance is the one kind or many in Ti, V, Mn, Fe, Co, Ni, Cu, Mo, Zn, Sn, Sb and W
Kind.
Further, described metal simple-substance is one or more in V, Fe, Co, Cu, Mo, Sn.
Further, described metal simple-substance is Fe and/or Sn.
Present invention also offers a kind of preparation method of anode material of lithium-ion battery as above, including following step
Suddenly：(1) with metal simple-substance, sulphur simple substance, selenium simple substance and/or tellurium simple substance are raw material, and it is mixed in proportion；(2) by step (1)
Mixture high temperature sintering under vacuum or inert gas conditions obtains described negative material.
Further, in step (2), described sintering temperature is 200~1000 DEG C, and sintering time is 5~100 hours, institute
Noble gases are stated for argon or nitrogen.
Further, described sintering temperature is 300~600 DEG C, and sintering time is 20~80 hours.
Further, described sintering temperature is 400 DEG C, and sintering time is 50 hours.
Present invention also offers a kind of sodium-ion battery negative pole with negative material as above as active substance, bag
Include：Negative material active substance, binding agent and conductive filler, wherein, described binding agent is Kynoar or carboxymethyl
Cellulose, described conductive filler is conductive carbon black or acetylene black, described negative material active substance, binding agent and conduction
The mass ratio of filler is 8:1:1.
Present invention also offers a kind of sodium-ion battery, including sodium-ion battery negative pole as above, with metallic sodium piece
As to electrode, using glass fibre as barrier film, with 1.0M NaCF3SO3Dissolve in diethylene glycol dimethyl ether as electrolyte group
Dress up battery.
Effect of the invention is that, using method of the present invention, have the advantage that and significant technique effect：
1st, method raw material of the present invention is easy to get, product yield close 100%；
2nd, method simple production process of the present invention, it is easy to operate, low production cost, is suitable to industrialized production；
3rd, method of the present invention is generated without waste liquid and toxic and harmful, and the pollution to environment is little；
4th, method of the present invention product good crystallinity at a sintering temperature, by-product is few；
5th, the pattern of product and granularity can be regulated and controled by the temperature and time of control reaction；
6th, the anode material of lithium-ion battery theoretical capacity height obtained by method of the present invention, electric conductivity is preferable,
Circulation and high rate performance are preferable.
The metal chalcogenide compound material prepared using the method for the invention can be widely applied to various science and skill
Art field, particularly for developing new anode material of lithium-ion battery and for designing new high selectivity solid catalysis
Agent.
Description of the drawings
Fig. 1 is the battery measurement result figure of the embodiment of the present invention 1；
Fig. 2 is the battery measurement result figure of the embodiment of the present invention 2；
Fig. 3 is the battery measurement result figure of the embodiment of the present invention 3；
Fig. 4 is the battery measurement result figure of the embodiment of the present invention 4；
Fig. 5 is the battery measurement result figure of the embodiment of the present invention 5；
Fig. 6 is the battery measurement result figure of the embodiment of the present invention 6；
Fig. 7 is the battery measurement result figure of the embodiment of the present invention 7；
Fig. 8 is the battery measurement result figure of the embodiment of the present invention 8；
Fig. 9 is the battery measurement result figure of the embodiment of the present invention 9；
Figure 10 is the battery measurement result figure of the embodiment of the present invention 10；
Figure 11 is the battery measurement result figure of the embodiment of the present invention 11；
Figure 12 is the battery measurement result figure of the embodiment of the present invention 12；
Figure 13 is the battery measurement result figure of the embodiment of the present invention 13；
Figure 14 is the battery measurement result figure of the embodiment of the present invention 14；
Figure 15 is the battery measurement result figure of the embodiment of the present invention 15；
Figure 16 is the battery measurement result figure of the embodiment of the present invention 16；
Figure 17 is the battery measurement result figure of the embodiment of the present invention 17；
Figure 18 is the battery measurement result figure of the embodiment of the present invention 18.
Specific embodiment
With reference to the accompanying drawings and detailed description the invention will be further described.
A kind of novel metal chalcogenide anode material of lithium-ion battery preparation method, comprises the following steps：
(1) with metal simple-substance, sulphur simple substance, selenium simple substance and/or tellurium simple substance are raw material, and it is mixed in proportion；Wherein, metal
The consumption of simple substance is 14%~80% (molar ratio, similarly hereinafter), and preferred scope is 25%~50%, and optimal ratio is
33%.After fixed metallic element ratio, remaining is sulphur simple substance, selenium simple substance and/or tellurium simple substance, sulphur simple substance, selenium simple substance and/or tellurium
The ratio of simple substance can be adjusted arbitrarily.
(2) mixture in step (1) is obtained into product under vacuum or inert gas conditions in high temperature sintering；It is resulting
Product degree of crystallinity preferably, products pure, impurity and by-product it is little.
Product in step (2) and binding agent and conductive filler are mixed, after being dried sodium-ion battery negative pole is obtained；Its
In, described binding agent is Kynoar or carboxymethyl cellulose, and described conductive filler is conductive carbon black or acetylene
Black, the mass ratio of described negative material active substance, binding agent and conductive filler is 8:1:1.
Then using metallic sodium piece as to electrode, using glass fibre as barrier film, with 1.0M NaCF3SO3Dissolve in diethyl two
Sodium-ion battery is assembled in diethylene glycol dimethyl ether as electrolyte.
In the present embodiment, the metal simple-substance described in step (1) be Ti, V, Mn, Fe, Co, Ni, Cu, Mo, Zn, Sn, Sb and
One or more in W, it is preferred to use one or more in V, Fe, Co, Cu, Mo, Sn, it is optimal with Fe and/or Sn.Described
Raw material can hand-ground or mechanical ball milling mixing.
In step (2), the noble gases are argon or nitrogen, and the sintering temperature is 200~1000 DEG C, during sintering
Between 5-100 hours.As a rule, sintering time is bad less than 5 hours effects, higher than 100 hours without practical significance.Preferably
Sintering temperature is 300~600 DEG C；Preferred sintering time is 20~80 hours；Optimal sintering temperature is 400 DEG C, optimal
Sintering time is 50 hours.
Embodiment 1
This example using the SnSSe materials that prepared by the use of solid-phase sintering technology as a example by the negative material of sodium-ion battery, tool
The battery preparation technique of body is:
(1) with Sn simple substance, S simple substance and Se simple substance are raw material, by 1:1:1 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product SnSSe in 50 hours in 400 DEG C of sintering under vacuum；
A) with 80wt%SnSSe materials as negative electrode active material, 10wt%CMC (carboxymethylcellulos, carboxylic
Methylcellulose) material as negative material binding agent, 10wt% conductive carbon blacks as negative material conductive filler, with metallic sodium
Piece as to electrode, using glass fibre as barrier film, 1.0M NaCF3SO3Dissolve in DEGDME (diethylene glycol
dimethyl ether；Diethylene glycol dimethyl ether) as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.1-3V, the use of test electric current density is 8000mA/g.Obtain result as shown in Figure 1.Having obtained battery capacity is：
252mAh/g, battery capacity conservation rate is 100% after circulating 1000 times.
Embodiment 2
This example using the SnSSe materials that prepared by the use of solid-phase sintering technology as a example by the negative material of sodium-ion battery, tool
The battery preparation technique of body is:
(1) with Sn simple substance, S simple substance and Se simple substance are raw material, by 1:1:1 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product SnSSe in 50 hours in 200 DEG C of sintering under vacuum；
A) with 80wt%SnSSe materials as negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film,
1.0M NaCF3SO3DEGDME is dissolved in as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.1-3V, the use of test electric current density is 6000mA/g.Obtain result as shown in Figure 2.Having obtained battery capacity is：
216mAh/g, battery capacity conservation rate is 98% after circulating 1000 times.
Embodiment 3
This example using the SnSSe materials that prepared by the use of solid-phase sintering technology as a example by the negative material of sodium-ion battery, tool
The battery preparation technique of body is:
(1) with Sn simple substance, S simple substance and Se simple substance are raw material, by 1:1:1 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product SnSSe in 50 hours in 1000 DEG C of sintering under vacuum；
A) with 80wt%SnSSe materials as negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film,
1.0M NaCF3SO3DEGDME is dissolved in as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.1-3V, the use of test electric current density is 5000mA/g.Obtain result as shown in Figure 2.Having obtained battery capacity is：
223mAh/g, battery capacity conservation rate is 100% after circulating 1000 times.
Embodiment 4
This example using the SnSSe materials that prepared by the use of solid-phase sintering technology as a example by the negative material of sodium-ion battery, tool
The battery preparation technique of body is:
(1) with Sn simple substance, S simple substance and Se simple substance are raw material, by 1:1:1 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product SnSSe in 50 hours in 400 DEG C of sintering under a nitrogen atmosphere；
A) with 80wt%SnSSe materials as negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film,
1.0M NaCF3SO3DEGDME is dissolved in as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.1-3V, the use of test electric current density is 2000mA/g.Obtain result as shown in Figure 2.Having obtained battery capacity is：
376mAh/g, battery capacity conservation rate is 99% after circulating 500 times.
Embodiment 5
This example using the SnSSe materials that prepared by the use of solid-phase sintering technology as a example by the negative material of sodium-ion battery, tool
The battery preparation technique of body is:
(1) with Sn simple substance, S simple substance and Se simple substance are raw material, by 1:1:1 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product SnSSe in 5 hours in 400 DEG C of sintering under vacuum；
A) with 80wt%SnSSe materials as negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film,
1.0M NaCF3SO3DEGDME is dissolved in as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.1-3V, the use of test electric current density is 1000mA/g.Obtain result as shown in Figure 2.Having obtained battery capacity is：
340mAh/g, battery capacity conservation rate is 81% after circulating 300 times.
Embodiment 6
This example using the SnSSe materials that prepared by the use of solid-phase sintering technology as a example by the negative material of sodium-ion battery, tool
The battery preparation technique of body is:
(1) with Sn simple substance, S simple substance and Se simple substance are raw material, by 1:1:1 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product SnSSe in 100 hours in 400 DEG C of sintering under vacuum；
A) with 80wt%SnSSe materials as negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film,
1.0M NaCF3SO3DEGDME is dissolved in as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.1-3V, the use of test electric current density is 5000mA/g.Obtain result as shown in Figure 2.Having obtained battery capacity is：
338mAh/g, battery capacity conservation rate is 100% after circulating 300 times.
Embodiment 7
SnS of this example to be prepared using solid-phase sintering technology2As a example by material is as the negative material of sodium-ion battery, specifically
Battery preparation technique be:
(1) with Sn simple substance and S simple substance as raw material, by 1:2 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product SnS in 50 hours in 400 DEG C of sintering under vacuum2；
A) with 80wt%SnS2Material is negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film, with
1.0M NaCF3SO3Dissolve in DEGDME as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.25-3V, the use of test electric current density is 500mA/g.Obtain result as shown in Figure 7.Having obtained battery capacity is：
427mAh/g, battery capacity conservation rate is 94.6% after circulating 200 times.
Embodiment 8
SnSe of this example to be prepared using solid-phase sintering technology2As a example by material is as the negative material of sodium-ion battery, tool
The battery preparation technique of body is:
(1) with Sn simple substance and Se simple substance as raw material, by 1:2 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product SnSe in 50 hours in 400 DEG C of sintering under vacuum2；
A) with 80wt%SnSe2Material is negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film, with
1.0M NaCF3SO3Dissolve in DEGDME as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.5-3V, the use of test electric current density is 100mA/g.Obtain result as shown in Figure 8.Having obtained battery capacity is：
200mAh/g, battery capacity conservation rate is 100% after circulating 50 times..
Embodiment 9
This example using the SnS materials that prepared by the use of solid-phase sintering technology as a example by the negative material of sodium-ion battery, specifically
Battery preparation technique be:
(1) with Sn simple substance and S simple substance as raw material, by 1:1 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product SnS in 50 hours in 400 DEG C of sintering under vacuum；
A) with 80wt%SnS2Material is negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film, with
1.0M NaCF3SO3Dissolve in DEGDME as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.1-3V, the use of test electric current density is 3000mA/g.Obtain result as shown in Figure 7.Having obtained battery capacity is：
162mAh/g, battery capacity conservation rate is 76% after circulating 200 times.
Embodiment 10
This example using the SnSe materials that prepared by the use of solid-phase sintering technology as a example by the negative material of sodium-ion battery, specifically
Battery preparation technique be:
(1) with Sn simple substance and Se simple substance as raw material, by 1:1 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product SnSe in 50 hours in 400 DEG C of sintering under vacuum；
A) with 80wt%SnSe materials as negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film, with
1.0M NaCF3SO3Dissolve in DEGDME as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.05-3V, the use of test electric current density is 100mA/g.Obtain result as shown in Figure 10.Having obtained battery capacity is：
327mAh/g, battery capacity conservation rate is 66.9% after circulating 50 times.
Embodiment 11
MoS of this example to be prepared using solid-phase sintering technology2As a example by material is as the negative material of sodium-ion battery, specifically
Battery preparation technique be:
(1) with Mo simple substance and S simple substance as raw material, by 1:2 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product MoS in 50 hours in 400 DEG C of sintering under vacuum2；
A) with 80wt%MoS2Material is negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film, with
1.0M NaCF3SO3Dissolve in DEGDME as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.2-3V, the use of test electric current density is 1000mA/g.Obtain result as shown in figure 11.Having obtained battery capacity is：
313mAh/g, battery capacity conservation rate is 100% after circulating 200 times.
Embodiment 12
MoS of this example to be prepared using solid-phase sintering technology6As a example by material is as the negative material of sodium-ion battery, specifically
Battery preparation technique be:
(1) with Mo simple substance and S simple substance as raw material, by 1:6 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product MoS in 50 hours in 400 DEG C of sintering under vacuum6；
A) with 80wt%MoS6Material is negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film, with
1.0M NaCF3SO3Dissolve in DEGDME as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.2-3V, the use of test electric current density is 1000mA/g.Obtain result as shown in figure 11.Having obtained battery capacity is：
299mAh/g, battery capacity conservation rate is 100% after circulating 190 times.
Embodiment 13
Cu of this example to be prepared using solid-phase sintering technology4As a example by S material is as the negative material of sodium-ion battery, specifically
Battery preparation technique be:
(1) with Cu simple substance and S simple substance as raw material, by 4:1 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product Cu in 50 hours in 400 DEG C of sintering under vacuum4S；
A) with 80wt%Cu4S material is negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film, with
1.0M NaCF3SO3Dissolve in DEGDME as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.01-3V, the use of test electric current density is 100mA/g.Obtain result as shown in figure 13.Having obtained battery capacity is：
205mAh/g, battery capacity conservation rate is 94% after circulating 100 times.
Embodiment 14
This example using the FeS materials that prepared by the use of solid-phase sintering technology as a example by the negative material of sodium-ion battery, specifically
Battery preparation technique be:
(1) with Fe simple substance and S simple substance as raw material, by 1:1 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product FeS in 80 hours under the conditions of argon in 300 DEG C of sintering；
A) with 80wt%FeS materials as negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film, with
1.0M NaCF3SO3Dissolve in DEGDME as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.5-3V, the use of test electric current density is 1000mA/g.Obtain result as shown in figure 13.Having obtained battery capacity is：
325mAh/g, battery capacity conservation rate is 97% after circulating 300 times.
Embodiment 15
This example using the FeSe materials that prepared by the use of solid-phase sintering technology as a example by the negative material of sodium-ion battery, specifically
Battery preparation technique be:
(1) with Fe simple substance and Se simple substance as raw material, by 1:1 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product FeSe in 20 hours in 600 DEG C of sintering under vacuum；
A) with 80wt%FeSe materials as negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film, with
1.0M NaCF3SO3Dissolve in DEGDME as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.5-3V, the use of test electric current density is 300mA/g.Obtain result as shown in figure 13.Having obtained battery capacity is：
326mAh/g, battery capacity conservation rate is 99% after circulating 200 times.
Embodiment 16
FeSnS of this example to be prepared using solid-phase sintering technology2As a example by material is as the negative material of sodium-ion battery, tool
The battery preparation technique of body is:
(1) with Fe simple substance, Sn simple substance and S simple substance are raw material, by 1:1:2 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product FeSnS in 50 hours in 400 DEG C of sintering under vacuum2；
A) with 80wt%FeSnS2Material is negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film, with
1.0M NaCF3SO3Dissolve in DEGDME as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.5-3V, the use of test electric current density is 1000mA/g.Obtain result as shown in figure 13.Having obtained battery capacity is：
345mAh/g, battery capacity conservation rate is 100% after circulating 200 times.
Embodiment 17
FeCoS of this example to be prepared using solid-phase sintering technology2As a example by material is as the negative material of sodium-ion battery, tool
The battery preparation technique of body is:
(1) with Fe simple substance, Co simple substance and S simple substance are raw material, by 1:1:2 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product FeCoS in 50 hours in 400 DEG C of sintering under vacuum2；
A) with 80wt%FeCoS2Material is negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film, with
1.0M NaCF3SO3Dissolve in DEGDME as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.5-3V, the use of test electric current density is 300mA/g.Obtain result as shown in figure 13.Having obtained battery capacity is：
375mAh/g, battery capacity conservation rate is 100% after circulating 200 times.
Embodiment 18
This example using the FeTe materials that prepared by the use of solid-phase sintering technology as a example by the negative material of sodium-ion battery, specifically
Battery preparation technique be:
(1) with Fe simple substance and Te simple substance as raw material, by 1:1 ratio (mol ratio) is ground；
(2) mixture in step (1) is obtained into product FeTe in 50 hours in 400 DEG C of sintering under vacuum；
A) with 80wt%FeTe materials as negative electrode active material, 10wt%CMC materials as negative material binding agent,
10wt% conductive carbon blacks as negative material conductive filler, using metallic sodium piece as to electrode, using glass fibre as barrier film, with
1.0M NaCF3SO3Dissolve in DEGDME as electrolyte.
B) button cell is assembled into as both positive and negative polarity using above-mentioned material, carries out battery performance test.Using test voltage
Scope is 0.5-3V, the use of test electric current density is 300mA/g.Obtain result as shown in figure 13.Having obtained battery capacity is：
229mAh/g, battery capacity conservation rate is 100% after circulating 50 times.
The data summary table of above-described embodiment 1-18 is as follows：
By above-described embodiment as can be seen that on the basis of non-composite material and preparation are simple, the present invention passes through will list
The cell negative electrode material that material (metal simple-substance and sulfur family simple substance) solid-phase sintering method is obtained has the potentiality of large-scale production,
And show good storage sodium performance.Compared with some material with carbon elements, the electrode material in above-described embodiment has higher appearance
Amount output.Compared with the anode material of lithium-ion battery delivered, the higher capacity of electrode material in above-described embodiment keeps
Rate.
Above content is to combine specific embodiment further description made for the present invention, it is impossible to assert this
It is bright to be embodied as being confined to these explanations.For general technical staff of the technical field of the invention, do not taking off
On the premise of present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the protection of the present invention
Scope.
Claims (12)
1. a kind of anode material of lithium-ion battery, is characterized in that：Described negative material is by metal simple-substance and sulfur family simple substance in height
Solid-phase sintering is formed under conditions of warm vacuum or noble gases, wherein, the consumption of described metal simple-substance rubs for 14%~80%
That ratio, described sulfur family simple substance is sulphur simple substance, selenium simple substance and/or tellurium simple substance.
2. a kind of anode material of lithium-ion battery as claimed in claim 1, is characterized in that：The consumption of described metal simple-substance is
25%~50% molar ratio.
3. a kind of anode material of lithium-ion battery as claimed in claim 2, is characterized in that：The consumption of described metal simple-substance is
33% molar ratio.
4. a kind of anode material of lithium-ion battery as described in any one of claims 1 to 3, is characterized in that：Described metal list
Matter is one or more in Ti, V, Mn, Fe, Co, Ni, Cu, Mo, Zn, Sn, Sb and W.
5. a kind of anode material of lithium-ion battery as claimed in claim 4, is characterized in that：Described metal simple-substance be V, Fe,
One or more in Co, Cu, Mo, Sn.
6. a kind of anode material of lithium-ion battery as claimed in claim 5, is characterized in that：Described metal simple-substance be Fe and/
Or Sn.
7. a kind of preparation method of the anode material of lithium-ion battery as described in claim 1-6, comprises the following steps：(1) with
Metal simple-substance, sulphur simple substance, selenium simple substance and/or tellurium simple substance are raw material, and it is mixed in proportion；(2) mixture in step (1) is existed
High temperature sintering obtains described negative material under vacuum or inert gas conditions.
8. a kind of preparation method of anode material of lithium-ion battery as claimed in claim 7, is characterized in that：In step (2), institute
The sintering temperature stated is 200~1000 DEG C, and sintering time is 5~100 hours, and the noble gases are argon or nitrogen.
9. a kind of preparation method of anode material of lithium-ion battery as claimed in claim 8, is characterized in that：In step (2), institute
The sintering temperature stated is 300~600 DEG C, and sintering time is 20~80 hours.
10. a kind of preparation method of anode material of lithium-ion battery as claimed in claim 9, is characterized in that：In step (2),
Described sintering temperature is 400 DEG C, and sintering time is 50 hours.
A kind of sodium-ion battery negative pole of 11. negative materials with described in claim 1-6 as active substance, including：Negative pole material
Material active substance, binding agent and conductive filler, wherein, described binding agent is Kynoar or carboxymethyl cellulose, institute
The conductive filler stated is conductive carbon black or acetylene black, the matter of described negative material active substance, binding agent and conductive filler
Amount is than being 8:1:1.
A kind of 12. sodium-ion batteries, it is characterised in that：Including the sodium-ion battery negative pole described in claim 11, with metallic sodium
Piece as to electrode, using glass fibre as barrier film, with 1.0M NaCF3SO3Dissolve in diethylene glycol dimethyl ether as electrolyte
It is assembled into battery.
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| CN107017403A (en) * | 2017-06-07 | 2017-08-04 | 东莞市迈科新能源有限公司 | A kind of cell negative electrode material and preparation method thereof and its application |
| CN109935804A (en) * | 2019-01-09 | 2019-06-25 | 上海大学(浙江·嘉兴)新兴产业研究院 | A kind of long-life vulcanization tin negative pole material and preparation method thereof |
| CN114023942A (en) * | 2021-11-09 | 2022-02-08 | 赣南科技学院 | Reduced graphene oxide loaded FeTe composite material and preparation method and application thereof |
| CN114291840A (en) * | 2021-12-31 | 2022-04-08 | 杭州电子科技大学 | Two-dimensional adjustable SnSSe porous nanosheet and preparation and application thereof |
| CN115818588A (en) * | 2022-12-09 | 2023-03-21 | 山西大学 | Sodium ion battery negative electrode material based on carbon nanosheet carrier and preparation method thereof |
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| CN105514356A (en) * | 2015-12-25 | 2016-04-20 | 东莞威胜储能技术有限公司 | Composite cathode material for sodium battery and preparation method of composite cathode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107017403A (en) * | 2017-06-07 | 2017-08-04 | 东莞市迈科新能源有限公司 | A kind of cell negative electrode material and preparation method thereof and its application |
| CN109935804A (en) * | 2019-01-09 | 2019-06-25 | 上海大学(浙江·嘉兴)新兴产业研究院 | A kind of long-life vulcanization tin negative pole material and preparation method thereof |
| CN109935804B (en) * | 2019-01-09 | 2022-06-03 | 上海大学(浙江·嘉兴)新兴产业研究院 | Long-life tin sulfide negative electrode material and preparation method thereof |
| CN114023942A (en) * | 2021-11-09 | 2022-02-08 | 赣南科技学院 | Reduced graphene oxide loaded FeTe composite material and preparation method and application thereof |
| CN114291840A (en) * | 2021-12-31 | 2022-04-08 | 杭州电子科技大学 | Two-dimensional adjustable SnSSe porous nanosheet and preparation and application thereof |
| CN114291840B (en) * | 2021-12-31 | 2023-12-26 | 杭州电子科技大学 | Two-dimensional adjustable SnSSe porous nano-sheet and preparation and application thereof |
| CN115818588A (en) * | 2022-12-09 | 2023-03-21 | 山西大学 | Sodium ion battery negative electrode material based on carbon nanosheet carrier and preparation method thereof |
| CN115818588B (en) * | 2022-12-09 | 2024-03-12 | 山西大学 | Sodium ion battery negative electrode material based on carbon nano sheet carrier and preparation method thereof |
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Application publication date: 20170517 |