CN107978745A - A kind of high power capacity carbon nanotubes composite sulfuration cobalt negative material and its preparation and application - Google Patents
A kind of high power capacity carbon nanotubes composite sulfuration cobalt negative material and its preparation and application Download PDFInfo
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- CN107978745A CN107978745A CN201711166653.7A CN201711166653A CN107978745A CN 107978745 A CN107978745 A CN 107978745A CN 201711166653 A CN201711166653 A CN 201711166653A CN 107978745 A CN107978745 A CN 107978745A
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Abstract
The present invention discloses a kind of high power capacity carbon nanotubes composite sulfuration cobalt negative material and preparation method and application, belongs to technical field of lithium ion.Hydrolysis occur for the crystallization water that the present invention is contained using Cobalt diacetate tetrahydrate itself and cobalt acetate generate bar-shaped to contain cobalt precursor, in addition under the action of PVP, size containing cobalt precursor is limited, the bar-shaped presoma of Nano grade is obtained, the cobalt sulfide of TAA and forerunner's precursor reactant generation nano bar-shape, the crystal property of material can be improved in follow-up sintering process, the nano material for being uniformly compounded with carbon nanotubes is conducive to the reduction of internal resistance and the transmission of electronics, improves a lot to chemical property.Present invention uses Freeze Drying Technique, effectively prevent the problem of carbon nanotubes is easily reunited.The compound CoS negative materials of obtained carbon nanotubes have high specific capacity, and charge/discharge capacity is high, and coulombic efficiency is high first, and capacity attenuation situation significantly improves.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of high power capacity carbon nanotubes composite sulfuration cobalt anode
Material and preparation method and application.
Background technology
Lithium ion battery because its operating voltage height, specific capacity height, good cycle, quickly-chargeable, without note effect, green
The advantages that environmentally friendly, be widely applied in many fields.The lithium ion battery of commercialization is still using carbon materials as anode
Material, but capacity of the material in actual battery is relatively low (theoretical capacity is only 372mAh/g), has been unable to meet the need of people
Ask.Therefore, development of negative material of the research and development with higher capacity for lithium ion battery has great importance.Due to transition
Metal sulfide (MoS2, FeS, NiS, CoS2Deng) there is very high specific capacity, applied the research in lithium ion battery
It is more and more.Wherein, there is the cobalt sulfide (Co of a variety of stoichiometric ratios1-xS, CoS, CoS2, Co3S4Deng) because of its unique electrification
Learn characteristic and cause the interest of many researchers.In the research of numerous lithium ion battery cobalt sulfide negative materials, due to lithium
The insertion and abjection of ion, the volume of electrode material can expand, or even dusting, cause structure collapses, and in discharge and recharge
During can generate irreversible simple substance cobalt, so as to reduce the reversible capacity and cyclical stability of electrode material.Fortunately,
By control synthesize special pattern, structure can alleviate stress variation in charge and discharge process, reduce volumetric expansion, by with
Carbon nanotubes or graphene etc. are compound can to improve the electric conductivity and cyclical stability of material, so as to significantly improve its electrochemistry
Performance.
The content of the invention
The shortcomings that in order to overcome the prior art and deficiency, primary and foremost purpose of the invention are that providing one kind is used for lithium-ion electric
The preparation method of the high power capacity carbon nanotubes composite sulfuration cobalt negative material in pond.
Another object of the present invention is to provide the height for lithium ion battery being prepared by above-mentioned preparation method
Capacity carbon nanotubes composite sulfuration cobalt negative material.
It is still another object of the present invention to provide the above-mentioned high power capacity carbon nanotubes composite sulfuration cobalt for lithium ion battery
The application of negative material.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of high-capacity lithium ion cell cobalt sulfide negative material, comprises the following steps：
(1) in the case where rotating speed is the stirring condition of 400~700rpm, polyvinylpyrrolidone (PVP) is solved homogeneously in into nothing
In water-ethanol, become to solution and clarify；
(2) in the case where rotating speed is the stirring condition of 400~700rpm, by Cobalt diacetate tetrahydrate (Co (CH3COO)2·4H2O) add
Into the solution of step (1), at ambient temperature persistently stir 20~40min, after cobalt acetate is uniformly dispersed stand 40~
50h, obtains precipitating containing cobalt precursor；
(3) solution of generation precipitation in step (2) is centrifuged, removes reusable heat ethanol washing 10~20 after supernatant
Obtain containing cobalt precursor after secondary；
(4) will obtain drying containing cobalt precursor in step (3)；
(5) under continuous agitation, by a certain proportion of nothing is added to containing cobalt precursor, thioacetamide (TAA)
In water-ethanol, under conditions of speed of agitator is 600~800rpm, 30~40min (being preferably 35~40min) is persistently stirred
Afterwards, it is completely dissolved it；
(6) solution in step (5) is transferred in inner liner of reaction kettle, liner is put into stainless steel cauldron, 110
5~8h of constant temperature obtains cobalt sulfide (CoS) under conditions of~160 DEG C；
(7) 4~6h is calcined under the conditions of CoS being placed in 400~600 DEG C and improves its crystallinity.
Preferably, the concentration of polyvinylpyrrolidone (PVP) is 15~25g/L in the solution described in step (1)；
Specifically, absolute ethyl alcohol is 200mL, when PVP is 3~5g, absolute ethyl alcohol can be dissolved.
Preferably, polyvinylpyrrolidone (PVP) the K values described in step (1) are a kind of non-ionic height for 30, PVP
Molecular compound.
Preferably, the mass ratio of the Cobalt diacetate tetrahydrate described in step (2) and polyvinylpyrrolidone is (1~2)：(3~
5)。
Preferably, the time persistently stirred at ambient temperature described in step (2) is 20~35min；
Preferably, the condition of the drying described in step (4) is 60~80 DEG C of dry 2~6h；
Preferably, the mass ratio containing cobalt precursor and thioacetamide (TAA) described in step (5) is (7~9)：(10
~12.5).
A kind of preparation method of high power capacity carbon nanotubes composite sulfuration cobalt negative material for lithium ion battery, including with
Lower step：
(A) carbon nanotubes is added in dust technology, ultrasound, under conditions of rotating speed is 400~700rpm, is continued
Stirring, above-mentioned solution is heated；
(B) solution in step (A) is filtered to obtain carbon nanotubes, it is added in concentrated nitric acid, be 400 in rotating speed
Under conditions of~700rpm, carry out continuing stirring, above-mentioned solution is heated, filtering and washing after the solution dilution after reaction obtains
Carbon nanotubes after to oxidation；
(C) carbon nanotubes after the oxidation that will be obtained in step (B) is freeze-dried；
(D) in the case where rotating speed is the lasting stirring condition of 600~800rpm, the CoS after calcining in above-mentioned steps (7) is added
Into absolute ethyl alcohol, the carbon nanotubes after oxidation is added into above-mentioned solution, persistently stirs 40min~60min；
(E) solution after stirring in step (D) is filtered, carbon nanotubes composite sulfuration cobalt is obtained after freeze-drying and is born
Pole material.
Preferably, the condition of the heating described in step (A) is to be heated to 60~80 DEG C and 2~4h of constant temperature；
Preferably, the concentration of carbon nanotubes is 1~3g/L in the solution described in step (A)；
Preferably, the concentration of the dust technology described in step (A) is 1~3mol/L；
Preferably, the concentrated nitric acid described in step (B) is 65%~68% concentrated nitric acid；
Preferably, the condition of the heating described in step (B) is to be heated to 60~80 DEG C and 4~6h of constant temperature；
Preferably, the solution after reaction is diluted to by 8~12 times of solution dilution after reaction described in step (B)；
Preferably, the time of the freeze-drying described in step (C) is 48~52h；
Preferably, the concentration of cobalt sulfide is 1.6~2g/L in the solution described in step (D).
The mass ratio of carbon nanotubes after the cobalt sulfide and oxidation is (16~20)：(1~2).
A kind of high power capacity carbon nanotubes composite sulfuration cobalt negative material for lithium ion battery, passes through above-mentioned preparation method
It is prepared.
The high power capacity carbon nanotubes composite sulfuration cobalt negative material for lithium ion battery is in manufacture lithium ion battery
In application.
The principle of the present invention is：The crystallization water that Cobalt diacetate tetrahydrate itself contains and cobalt acetate generation hydrolysis generation are bar-shaped
Contain cobalt precursor, in addition under the action of PVP, the size containing cobalt precursor is limited, obtained Nano grade it is bar-shaped before
Body is driven, TAA generates the cobalt sulfide of nano bar-shape with forerunner's precursor reactant, and the crystallinity of material can be improved in follow-up sintering process
Can, the nano material for being uniformly compounded with carbon nanotubes is conducive to the reduction of internal resistance and the transmission of electronics, has very to chemical property
Big raising.
The present invention is had the following advantages relative to the prior art and effect：
(1) present invention introduces PVP, scantling can be limited well.
(2) present invention uses Freeze Drying Technique, it effectively prevent the problem of carbon nanotubes is easily reunited.
(3) the compound CoS negative materials of preparation method of the present invention obtains carbon nanotubes have high specific capacity, discharge and recharge
Capacity is high, and coulombic efficiency is high first, and capacity attenuation situation significantly improves.In addition carbon nanotubes improves the electronics of material
Electric conductivity, is conducive to improve kinetics performance, so that the chemical property of material is improved.
Brief description of the drawings
Fig. 1 is the figures of the SEM containing cobalt precursor prepared by embodiment 1.
Fig. 2 is the TEM figures of CoS prepared by embodiment 1.
Fig. 3 is the SEM figures of the CoS of composite carbon nanometer tube prepared by embodiment 1.
Fig. 4 is the CoS negative materials that the CoS negative materials of composite carbon nanometer tube prepared by embodiment 1 are prepared with comparative example
The lithium ion battery specific discharge capacity of making and the graph of a relation of the circulation number of turns.
Embodiment
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
A kind of preparation method of the compound CoS negative materials of high power capacity carbon nanotubes for lithium ion battery, including it is following
Step：
First, the preparation of cobalt sulfide：
(1) in the case where rotating speed is the stirring condition of 500rpm, the polyvinylpyrrolidone (PVP) of 3g is solved homogeneously in
In 200mL absolute ethyl alcohols, become to solution and clarify.
(2) in the case where rotating speed is the stirring condition of 600rpm, by 1.28g Cobalt diacetate tetrahydrates (Co (CH3COO)2·4H2O) add
Into above-mentioned solution, 20min is persistently stirred at ambient temperature, 48h is stood after cobalt acetate is uniformly dispersed, and obtains containing cobalt precursor
Body precipitates.
(3) solution of generation precipitation in step (2) is centrifuged, after reusable heat ethanol washs 10 times after removing supernatant
Obtain containing cobalt precursor.
(4) will obtain being put into 60 DEG C of baking ovens dry 2h containing cobalt precursor in step (3).
(5) under continuous agitation, 0.16g is added to 80mL containing cobalt precursor, 0.2g thioacetamides (TAA)
In absolute ethyl alcohol, in the case where rotating speed is the stirring condition of 700rpm, after persistently stirring 40min, it is completely dissolved it.
(6) solution in step (5) is transferred in inner liner of reaction kettle, liner is put into stainless steel cauldron, 120
Constant temperature 6h obtains CoS under conditions of DEG C.
(7) 5h is calcined under the conditions of CoS being placed in 450 DEG C and improves its crystallinity.
2nd, cobalt sulfide and carbon nanotubes is compound：
(8) 0.4g carbon nanotubes is added in 200mL 3mol/L dust technologies, ultrasonic 1h, in the bar that rotating speed is 500rpm
Under part, carry out continuing stirring, heat the solution to 60 DEG C and constant temperature 4h.
(9) solution in step (8) is filtered to obtain carbon nanotubes, it is added to 200mL concentrated nitric acids (65%~
68%) in, under conditions of rotating speed is 700rpm, carries out continuing stirring, heat the solution to 60 DEG C and constant temperature 4h, will be anti-
Filtering and washing after solution after answering dilutes 10 times, the carbon nanotubes after being aoxidized.
(10) carbon nanotubes after the oxidation that will be obtained in step (9) carries out freeze-drying 48h.
(11) in the case where rotating speed is the lasting stirring condition of 600rpm, 0.08g is taken to add the CoS after calcining in step (7)
Into 50mL absolute ethyl alcohols, the carbon nanotubes after 5mg oxidations is added into above-mentioned solution, persistently stirs 40min.
(12) solution after stirring in step (11) is filtered, the compound CoS of carbon nanotubes is obtained after freeze-drying
Negative material.
Fig. 1 is the figures of the SEM containing cobalt precursor prepared by embodiment 1.The forerunner that method obtains thus is planted as seen from Figure 1
Body is bar-shaped, and length is largely focused on 1~2 μm or so.
Fig. 2 is the TEM figures of CoS prepared by embodiment 1.The wall for the bar-shaped CoS that method obtains thus is planted as seen from Figure 2
Thickness is largely focused on 40~60nm or so.
Fig. 3 is the SEM figures of the CoS of composite carbon nanometer tube prepared by embodiment 1.Carbon nanotubes and rod as seen from Figure 3
Shape CoS is more uniform compound.
Embodiment 2
A kind of preparation method of the compound CoS negative materials of high power capacity carbon nanotubes for lithium ion battery, including it is following
Step：
First, the preparation of cobalt sulfide：
(1) in the case where rotating speed is the stirring condition of 700rpm, the polyvinylpyrrolidone (PVP) of 4g is solved homogeneously in
In 200mL absolute ethyl alcohols, become to solution and clarify.
(2) in the case where rotating speed is the stirring condition of 500rpm, by 1.5g Cobalt diacetate tetrahydrates (Co (CH3COO)2·4H2O) add
Into above-mentioned solution, 30min is persistently stirred at ambient temperature, 40h is stood after cobalt acetate is uniformly dispersed, and obtains containing cobalt precursor
Body precipitates.
(3) solution of generation precipitation in step (2) is centrifuged, after reusable heat ethanol washs 15 times after removing supernatant
Obtain containing cobalt precursor.
(4) will obtain being put into 80 DEG C of baking ovens dry 2h containing cobalt precursor in step (3).
(5) under continuous agitation, 0.18g is added to containing cobalt precursor, 0.25g thioacetamides (TAA)
In 80mL absolute ethyl alcohols, in the case where rotating speed is the stirring condition of 600rpm, after persistently stirring 40min, it is completely dissolved it.
(6) solution in step (5) is transferred in inner liner of reaction kettle, liner is put into stainless steel cauldron, 110
Constant temperature 6h obtains CoS under conditions of DEG C.
(7) 6h is calcined under the conditions of CoS being placed in 500 DEG C and improves its crystallinity.
2nd, cobalt sulfide and carbon nanotubes is compound：
(8) 0.4g carbon nanotubes is added in 200mL 2mol/L dust technologies, ultrasonic 1h, in the bar that rotating speed is 700rpm
Under part, carry out continuing stirring, heat the solution to 80 DEG C and constant temperature 2h.
(9) solution in step (8) is filtered to obtain carbon nanotubes, it is added to 200mL concentrated nitric acids (65%~
68%) in, under conditions of rotating speed is 400rpm, carries out continuing stirring, heat the solution to 80 DEG C and constant temperature 4h, will be anti-
Filtering and washing after solution after answering dilutes 8 times, the carbon nanotubes after being aoxidized.
(10) carbon nanotubes after the oxidation that will be obtained in step (9) carries out freeze-drying 50h.
(11) in the case where rotating speed is the lasting stirring condition of 800rpm, 0.1g is taken to be added to the CoS after calcining in step (7)
In 50mL absolute ethyl alcohols, the carbon nanotubes after 5mg oxidations is added into above-mentioned solution, persistently stirs 50min.
(12) solution after stirring in step (11) is filtered, the compound CoS of carbon nanotubes is obtained after freeze-drying
Negative material.
Embodiment 3
A kind of preparation method of the compound CoS negative materials of high power capacity carbon nanotubes for lithium ion battery, including it is following
Step：
First, the preparation of cobalt sulfide：
(1) in the case where rotating speed is the stirring condition of 400rpm, the polyvinylpyrrolidone (PVP) of 4g is solved homogeneously in
In 200mL absolute ethyl alcohols, become to solution and clarify.
(2) in the case where rotating speed is the stirring condition of 700rpm, by 1g Cobalt diacetate tetrahydrates (Co (CH3COO)2·4H2O) it is added to
In above-mentioned solution, 30min is persistently stirred at ambient temperature, 48h is stood after cobalt acetate is uniformly dispersed, and obtains containing cobalt precursor
Precipitation.
(3) solution of generation precipitation in step (2) is centrifuged, after reusable heat ethanol washs 15 times after removing supernatant
Obtain containing cobalt precursor.
(4) will obtain being put into 60 DEG C of baking ovens dry 4h containing cobalt precursor in step (3).
(5) under continuous agitation, 0.14g is added to 80mL containing cobalt precursor, 0.2g thioacetamides (TAA)
In absolute ethyl alcohol, in the case where rotating speed is the stirring condition of 600rpm, after persistently stirring 40min, it is completely dissolved it.
(6) solution in step (5) is transferred in inner liner of reaction kettle, liner is put into stainless steel cauldron, 140
Constant temperature 6h obtains CoS under conditions of DEG C.
(7) 4h is calcined under the conditions of CoS being placed in 600 DEG C and improves its crystallinity.
2nd, cobalt sulfide and carbon nanotubes is compound：
(8) 0.2g carbon nanotubes is added in 200mL 1mol/L dust technologies, ultrasonic 1h, in the bar that rotating speed is 400rpm
Under part, carry out continuing stirring, heat the solution to 70 DEG C and constant temperature 3h.
(9) solution in step (8) is filtered to obtain carbon nanotubes, it is added to 200mL concentrated nitric acids (65%~
68%) in, under conditions of rotating speed is 700rpm, carries out continuing stirring, heat the solution to 60 DEG C and constant temperature 6h, will be anti-
Filtering and washing after solution after answering dilutes 10 times, the carbon nanotubes after being aoxidized.
(10) carbon nanotubes after the oxidation that will be obtained in step (9) carries out freeze-drying 52h.
(11) in the case where rotating speed is the lasting stirring condition of 700rpm, 0.09g is taken to add the CoS after calcining in step (7)
Into 50mL absolute ethyl alcohols, the carbon nanotubes after 8mg oxidations is added into above-mentioned solution, persistently stirs 60min.
(12) solution after stirring in step (11) is filtered, the compound CoS of carbon nanotubes is obtained after freeze-drying
Negative material.
Embodiment 4
A kind of preparation method of the compound CoS negative materials of high power capacity carbon nanotubes for lithium ion battery, including it is following
Step：
First, the preparation of cobalt sulfide：
(1) in the case where rotating speed is the stirring condition of 600rpm, the polyvinylpyrrolidone (PVP) of 5g is solved homogeneously in
In 200mL absolute ethyl alcohols, become to solution and clarify.
(2) in the case where rotating speed is the stirring condition of 400rpm, by 2g Cobalt diacetate tetrahydrates (Co (CH3COO)2·4H2O) it is added to
In above-mentioned solution, 35min is persistently stirred at ambient temperature, 50h is stood after cobalt acetate is uniformly dispersed, and obtains containing cobalt precursor
Precipitation.
(3) solution of generation precipitation in step (2) is centrifuged, after reusable heat ethanol washs 20 times after removing supernatant
Obtain containing cobalt precursor.
(4) will obtain being put into 60 DEG C of baking ovens dry 4h containing cobalt precursor in step (3).
(5) under continuous agitation, 0.16g is added to 80mL containing cobalt precursor, 0.2g thioacetamides (TAA)
In absolute ethyl alcohol, in the case where rotating speed is the stirring condition of 600rpm, after persistently stirring 35min, it is completely dissolved it.
(6) solution in step (5) is transferred in inner liner of reaction kettle, liner is put into stainless steel cauldron, 150
Constant temperature 8h obtains CoS under conditions of DEG C.
(7) 6h is calcined under the conditions of CoS being placed in 400 DEG C and improves its crystallinity.
2nd, cobalt sulfide and carbon nanotubes is compound：
(8) 0.6g carbon nanotubes is added in 200mL 3mol/L dust technologies, ultrasonic 1h, in the bar that rotating speed is 600rpm
Under part, carry out continuing stirring, heat the solution to 60 DEG C and constant temperature 4h.
(9) solution in step (8) is filtered to obtain carbon nanotubes, it is added to 200mL concentrated nitric acids (65%~
68%) in, under conditions of rotating speed is 600rpm, carries out continuing stirring, heat the solution to 70 DEG C and constant temperature 5h, will be anti-
Filtering and washing after solution after answering dilutes 12 times, the carbon nanotubes after being aoxidized.
(10) carbon nanotubes after the oxidation that will be obtained in step (9) carries out freeze-drying 50h.
(11) in the case where rotating speed is the lasting stirring condition of 600rpm, 0.1g is taken to be added to the CoS after calcining in step (7)
In 50mL absolute ethyl alcohols, the carbon nanotubes after 8mg oxidations is added into above-mentioned solution, persistently stirs 50min.
(12) solution after stirring in step (11) is filtered, the compound CoS of carbon nanotubes is obtained after freeze-drying
Negative material.
Embodiment 5
A kind of preparation method of the compound CoS negative materials of high power capacity carbon nanotubes for lithium ion battery, including it is following
Step：
First, the preparation of cobalt sulfide：
(1) in the case where rotating speed is the stirring condition of 700rpm, the polyvinylpyrrolidone (PVP) of 5g is solved homogeneously in
In 200mL absolute ethyl alcohols, become to solution and clarify.
(2) in the case where rotating speed is the stirring condition of 400rpm, by 1.7g Cobalt diacetate tetrahydrates (Co (CH3COO)2·4H2O) add
Into above-mentioned solution, 30min is persistently stirred at ambient temperature, 48h is stood after cobalt acetate is uniformly dispersed, and obtains containing cobalt precursor
Body precipitates.
(3) solution of generation precipitation in step (2) is centrifuged, after reusable heat ethanol washs 20 times after removing supernatant
Obtain containing cobalt precursor.
(4) will obtain being put into 60 DEG C of baking ovens dry 6h containing cobalt precursor in step (3).
(5) under continuous agitation, 0.17g is added to containing cobalt precursor, 0.23g thioacetamides (TAA)
In 80mL absolute ethyl alcohols, in the case where rotating speed is the stirring condition of 800rpm, after persistently stirring 40min, it is completely dissolved it.
(6) solution in step (5) is transferred in inner liner of reaction kettle, liner is put into stainless steel cauldron, 160
Constant temperature 6h obtains CoS under conditions of DEG C.
(7) 6h is calcined under the conditions of CoS being placed in 600 DEG C and improves its crystallinity.
2nd, cobalt sulfide and carbon nanotubes is compound：
(8) 0.4g carbon nanotubes is added in 200mL 2mol/L dust technologies, ultrasonic 1h, in the bar that rotating speed is 600rpm
Under part, carry out continuing stirring, heat the solution to 60 DEG C and constant temperature 4h.
(9) solution in step (8) is filtered to obtain carbon nanotubes, it is added to 200mL concentrated nitric acids (65%~
68%) in, under conditions of rotating speed is 600rpm, carries out continuing stirring, heat the solution to 80 DEG C and constant temperature 4h, will be anti-
Filtering and washing after solution after answering dilutes 8 times, the carbon nanotubes after being aoxidized.
(10) carbon nanotubes after the oxidation that will be obtained in step (9) carries out freeze-drying 48h.
(11) in the case where rotating speed is the lasting stirring condition of 600rpm, 0.1g is taken to be added to the CoS after calcining in step (7)
In 50mL absolute ethyl alcohols, the carbon nanotubes after 10mg oxidations is added into above-mentioned solution, persistently stirs 50min.
(12) solution after stirring in step (11) is filtered, the compound CoS of carbon nanotubes is obtained after freeze-drying
Negative material.
Embodiment 6
A kind of preparation method of the compound CoS negative materials of high power capacity carbon nanotubes for lithium ion battery, including it is following
Step：
First, the preparation of cobalt sulfide：
(1) in the case where rotating speed is the stirring condition of 600rpm, the polyvinylpyrrolidone (PVP) of 3g is solved homogeneously in
In 200mL absolute ethyl alcohols, become to solution and clarify.
(2) in the case where rotating speed is the stirring condition of 700rpm, by 1.28g Cobalt diacetate tetrahydrates (Co (CH3COO)2·4H2O) add
Into above-mentioned solution, 30min is persistently stirred at ambient temperature, 45h is stood after cobalt acetate is uniformly dispersed, and obtains containing cobalt precursor
Body precipitates.
(3) solution of generation precipitation in step (2) is centrifuged, after reusable heat ethanol washs 10 times after removing supernatant
Obtain containing cobalt precursor.
(4) will obtain being put into 60 DEG C of baking ovens dry 2h containing cobalt precursor in step (3).
(5) under continuous agitation, 0.18g is added to containing cobalt precursor, 0.25g thioacetamides (TAA)
In 80mL absolute ethyl alcohols, in the case where rotating speed is the stirring condition of 600rpm, after persistently stirring 40min, it is completely dissolved it.
(6) solution in step (5) is transferred in inner liner of reaction kettle, liner is put into stainless steel cauldron, 150
Constant temperature 5h obtains CoS under conditions of DEG C.
(7) 6h is calcined under the conditions of CoS being placed in 500 DEG C and improves its crystallinity.
2nd, cobalt sulfide and carbon nanotubes is compound：
(8) 0.6g carbon nanotubes is added in 200mL 2mol/L dust technologies, ultrasonic 1h, in the bar that rotating speed is 700rpm
Under part, carry out continuing stirring, heat the solution to 80 DEG C and constant temperature 4h.
(9) solution in step (8) is filtered to obtain carbon nanotubes, it is added to 200mL concentrated nitric acids (65%~
68%) in, under conditions of rotating speed is 400rpm, carry out under conditions of continuing stirring, heat the solution to 60 DEG C and perseverance
Warm 6h, filtering and washing after the solution after reaction is diluted 12 times, the carbon nanotubes after being aoxidized.
(10) carbon nanotubes after the oxidation that will be obtained in step (9) carries out freeze-drying 48h.
(11) in the case where rotating speed is the lasting stirring condition of 800rpm, 0.1g is taken to be added to the CoS after calcining in step (7)
In 50mL absolute ethyl alcohols, the carbon nanotubes after 10mg oxidations is added into above-mentioned solution, persistently stirs 50min.
(12) solution after stirring in step (11) is filtered, the compound CoS of carbon nanotubes is obtained after freeze-drying
Negative material.
Comparative example
(1) in the case where rotating speed is the stirring condition of 500rpm, the polyvinylpyrrolidone (PVP) of 3g is solved homogeneously in
In 200mL absolute ethyl alcohols, become to solution and clarify.
(2) in the case where rotating speed is the stirring condition of 600rpm, by 1.28g Cobalt diacetate tetrahydrates (Co (CH3COO)2·4H2O) add
Into above-mentioned solution, 20min is persistently stirred at ambient temperature, 48h is stood after cobalt acetate is uniformly dispersed, and obtains containing cobalt precursor
Body precipitates.
(3) solution of generation precipitation in step (2) is centrifuged, after reusable heat ethanol washs 10 times after removing supernatant
Obtain containing cobalt precursor.
(4) will obtain being put into 60 DEG C of baking ovens dry 2h containing cobalt precursor in step (3).
(5) under continuous agitation, 0.16g is added to 80mL containing cobalt precursor, 0.2g thioacetamides (TAA)
In absolute ethyl alcohol, in the case where rotating speed is the stirring condition of 700rpm, after persistently stirring 40min, it is completely dissolved it.
(6) solution in step (5) is transferred in inner liner of reaction kettle, liner is put into stainless steel cauldron, 120
Constant temperature 6h obtains CoS under conditions of DEG C.
(7) 5h is calcined under the conditions of CoS being placed in 450 DEG C and obtains CoS negative materials.
Test case
(1) half-cell assembles：Obtained by the compound CoS negative materials of carbon nanotubes prepared by embodiment 1 and comparative example
Negative material, respectively with acetylene black and PVDF in mass ratio 8:1:1 progress slurrying is simultaneously coated with, and is assembled into by anode of metal lithium sheet
Half-cell.
(2) charge-discharge test：Obtained by the compound CoS negative materials of carbon nanotubes prepared by embodiment 1 and comparative example
Negative material, the lithium ion battery of making carry out discharge and recharge under the constant current of 80mA/g.
Fig. 4 is the CoS negative materials that the CoS negative materials of composite carbon nanometer tube prepared by embodiment 1 are prepared with comparative example
The lithium ion battery specific discharge capacity of making and the graph of a relation of the circulation number of turns.The anode material that as seen from Figure 4 prepared by embodiment 1
Discharge capacity is 980.0mAh/g to material first, and first circle coulombic efficiency is 78%, and capacity attenuation situation significantly improves.Contrast
Discharge capacity is 892.4mAh/g to negative material prepared by example first, and first circle coulombic efficiency is 72%.Show to be compounded with carbon nanometer
The chemical property of the CoS negative materials of pipe is more excellent.
In addition, the CoS negative materials of the composite carbon nanometer tube of the gained of embodiment 2~6 are pressed with acetylene black and PVDF respectively
Mass ratio 8:1:1 progress slurrying is simultaneously coated with, and half-cell is assembled into by anode of metal lithium sheet；Then in the constant current of 80mA/g
Lower carry out charge-discharge test, is detected：
Discharge capacity is 925.1mAh/g to negative material prepared by embodiment 2 first, and first circle coulombic efficiency is 75%.
Discharge capacity is 894.5mAh/g to negative material prepared by embodiment 3 first, and first circle coulombic efficiency is 74%.
Discharge capacity is 884.4mAh/g to negative material prepared by embodiment 4 first, and first circle coulombic efficiency is 76%.
Discharge capacity is 904.6mAh/g to negative material prepared by embodiment 5 first, and first circle coulombic efficiency is 73%.
Discharge capacity is 917.7mAh/g to negative material prepared by embodiment 6 first, and first circle coulombic efficiency is 78%.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high-capacity lithium ion cell cobalt sulfide negative material, it is characterised in that comprise the following steps：
(1) in the case where rotating speed is the stirring condition of 400~700rpm, polyvinylpyrrolidone is solved homogeneously in absolute ethyl alcohol,
Become to solution and clarify；
(2) in the case where rotating speed is the stirring condition of 400~700rpm, Cobalt diacetate tetrahydrate is added in the solution of step (1), in room
20~40min is persistently stirred under the conditions of temperature, 40~50h is stood after cobalt acetate is uniformly dispersed, obtains precipitating containing cobalt precursor；
(3) solution of generation precipitation in step (2) is centrifuged, after reusable heat ethanol washs 10~20 times after removing supernatant
Obtain containing cobalt precursor；
(4) will obtain drying containing cobalt precursor in step (3)；
(5) under continuous agitation, it is added to a certain proportion of containing cobalt precursor, thioacetamide in absolute ethyl alcohol,
Under conditions of speed of agitator is 600~800rpm, after persistently stirring 30~40min, it is completely dissolved it；
(6) solution in step (5) is transferred in inner liner of reaction kettle, liner is put into stainless steel cauldron, 110~
5~8h of constant temperature obtains CoS under conditions of 160 DEG C；
(7) 4~6h is calcined under the conditions of CoS being placed in 400~600 DEG C and improves its crystallinity.
2. the preparation method of high-capacity lithium ion cell cobalt sulfide negative material according to claim 1, it is characterised in that：
The concentration of polyvinylpyrrolidone is 15~25g/L in solution described in step (1)；
The mass ratio of Cobalt diacetate tetrahydrate and polyvinylpyrrolidone described in step (2) is (1~2)：(3~5).
3. the preparation method of high-capacity lithium ion cell cobalt sulfide negative material according to claim 1, it is characterised in that：
The condition of drying described in step (4) is 60~80 DEG C of dry 2~6h；
The mass ratio containing cobalt precursor and thioacetamide described in step (5) is (7~9)：(10~12.5).
4. a kind of preparation method of high power capacity carbon nanotubes composite sulfuration cobalt negative material for lithium ion battery, its feature exist
In comprising the following steps：
(A) carbon nanotubes is added in dust technology, ultrasound, under conditions of rotating speed is 400~700rpm, is persistently stirred
Mix, above-mentioned solution is heated；
(B) solution in step (A) is filtered to obtain carbon nanotubes, it is added in concentrated nitric acid, rotating speed for 400~
Under conditions of 700rpm, carry out continuing stirring, above-mentioned solution is heated, filtering and washing after the solution dilution after reaction obtains
Carbon nanotubes after oxidation；
(C) carbon nanotubes after the oxidation that will be obtained in step (B) is freeze-dried；
(D) in the case where rotating speed is the lasting stirring condition of 600~800rpm, by claims 1 to 3 any one of them step (7)
Cobalt sulfide after middle calcining is added in absolute ethyl alcohol, adds the carbon nanotubes after oxidation into above-mentioned solution, lasting stirring
40min~60min；
(E) solution after stirring in step (D) is filtered, carbon nanotubes composite sulfuration cobalt anode material is obtained after freeze-drying
Material.
5. the system of the high power capacity carbon nanotubes composite sulfuration cobalt negative material according to claim 4 for lithium ion battery
Preparation Method, it is characterised in that：
The condition of heating described in step (A) is to be heated to 60~80 DEG C and 2~4h of constant temperature；
The concentration of carbon nanotubes is 1~3g/L in solution described in step (A).
6. the system of the high power capacity carbon nanotubes composite sulfuration cobalt negative material according to claim 4 for lithium ion battery
Preparation Method, it is characterised in that：
The concentration of dust technology described in step (A) is 1~3mol/L；
The concentrated nitric acid that concentrated nitric acid described in step (B) is 65%~68%.
7. the system of the high power capacity carbon nanotubes composite sulfuration cobalt negative material according to claim 4 for lithium ion battery
Preparation Method, it is characterised in that：
The condition of heating described in step (B) is to be heated to 60~80 DEG C and 4~6h of constant temperature；
The solution after reaction is diluted to by 8~12 times of solution dilution after reaction described in step (B)；
The time of freeze-drying described in step (C) is 48~52h.
8. the system of the high power capacity carbon nanotubes composite sulfuration cobalt negative material according to claim 4 for lithium ion battery
Preparation Method, it is characterised in that：
The concentration of cobalt sulfide is 1.6~2g/L in solution described in step (D)；
The mass ratio of carbon nanotubes after the cobalt sulfide and oxidation is (16~20)：(1~2).
9. a kind of high power capacity carbon nanotubes composite sulfuration cobalt negative material for lithium ion battery, it is characterised in that pass through right
It is required that 4~8 any one of them preparation methods are prepared.
10. the high power capacity carbon nanotubes composite sulfuration cobalt negative material for lithium ion battery described in claim 9 is manufacturing
Application in lithium ion battery.
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