CN106299316B - A kind of lithium ion battery and its negative electrode material and preparation method - Google Patents

A kind of lithium ion battery and its negative electrode material and preparation method Download PDF

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Publication number
CN106299316B
CN106299316B CN201610910361.9A CN201610910361A CN106299316B CN 106299316 B CN106299316 B CN 106299316B CN 201610910361 A CN201610910361 A CN 201610910361A CN 106299316 B CN106299316 B CN 106299316B
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lithium ion
ion battery
negative electrode
shell
stratum nucleare
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CN106299316A (en
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李宝华
李海
钱坤
罗丹
贺艳兵
刘冬青
李懿洋
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Shenzhen International Graduate School of Tsinghua University
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Shenzhen Graduate School Tsinghua University
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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 belongs to technical field of lithium ion more particularly to a kind of cathode material of lithium ion battery, the negative electrode material has the nucleocapsid structure comprising stratum nucleare and shell；The stratum nucleare is antimony oxide, and the shell is antimonous sulfide, and the mass ratio of the stratum nucleare and the shell is (0.4-5): 1.Compared with the existing technology, the material powder that the present invention is prepared has preferable uniformity, dispersibility, and preparation process is simple, cost of manufacture is cheap, experiment time-consuming is shorter, environmental pollution is smaller, yield is higher, has splendid industrial applications prospect.Lithium ion battery negative material first charge-discharge efficiency of the present invention is high, specific capacity height (reaches 900mAh/g for the first time, current commercialized graphite theoretical specific capacity is 372mAh/g), good cycle, it is low effectively to improve current lithium ion battery negative material first charge discharge efficiency, the problem of low specific capacity.

Description

A kind of lithium ion battery and its negative electrode material and preparation method
Technical field
Good, stable structure that the invention belongs to technical field of lithium ion more particularly to a kind of large specific surface area, uniformity Cathode material of lithium ion battery and preparation method thereof, and comprising the negative electrode material with high specific capacity and stable The lithium ion battery of chemical property.
Background technique
With the increasing of human society energy demand and the increasing of fossil fuel (coal, petroleum, natural gas) consumption Add and a series of human society industrialization problem of environmental pollutions of bring, find a kind of environmentally friendly green energy resource by Gradually attract people's attention.Lithium ion battery is broken due to energy density with higher, longer cycle life, lesser environment Bad property and lower-price characteristic have boundless application prospect in new energy field now.At present commercialization lithium from Sub- cell negative electrode material mainly uses carbon material, but its specific capacity is lower, limits it in high-power type lithium ion battery direction Application.Specific capacity is higher in order to obtain, and the bigger lithium ion battery negative material of energy density, people start target diversion The metal and its composite material of micro/nano level.Wherein, the one-dimensional and its composite construction micro-nano powder material of Sb and its compound Material obtains extensive concern due to specific capacity with higher.
One-dimensional and its composite construction micro-nano powder has unique optics, electricity, mechanical property due to its special construction Matter, in terms of battery material, the environmental protection, catalytic field, obtain relatively broad application in medical application.Preparation at present One-dimensional and its composite construction micro-nano powder method is broadly divided into physical method and chemical method two major classes, and wherein physical method is mainly wrapped Include inert gas evaporation method, explosion method, severe plastic deformation method, laser beam, machine-alloying etc.；Chemical method includes gas phase combustion Burn synthetic method, sol-gel method, organic liquid phase synthetic method etc..The material that above method obtains is imitated with significant quantum size It answers, small-size effect and macroscopic quantum dimensional effect, but its preparation process is complex, experimental period is long, low yield, experiment By-product contamination environment in the process, seriously hinders the real application research of micro Nano material.
Studies have shown that micro-nano powder material as lithium ion battery negative material have have extended cycle life, height ratio capacity The characteristics of.Present inventor is by concentrating on studies discovery: by the antimony oxide coated with antimonous sulfide as lithium from When sub- cell negative electrode material, there is preferable structural stability during lithium ion deintercalation, to ensure that the circulation of battery Service life significantly improves the chemical property of lithium ion battery.
Summary of the invention
It is an object of the present invention to: in view of the deficiencies of the prior art, and provide a kind of large specific surface area, uniformity Good, stable structure lithium ion battery negative material, using the lithium ion battery of the negative electrode material with high specific capacity and surely Fixed chemical property.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of cathode material of lithium ion battery, the negative electrode material have the nucleocapsid structure comprising stratum nucleare and shell；
The stratum nucleare is antimony oxide, and the shell is antimonous sulfide, the mass ratio of the stratum nucleare and the shell For (0.4-5): 1.
As a kind of improvement of cathode material of lithium ion battery of the present invention, the partial size of the stratum nucleare is 100nm~2 μm, The shell with a thickness of 50nm~0.5 μm.
As a kind of improvement of cathode material of lithium ion battery of the present invention, the specific surface area of the negative electrode material is 200- 500m2g-1, the micro-shape of the stratum nucleare is rodlike, spherical, sea urchin shape, cruciformity or flower-shaped.
Compared with the existing technology, the present invention mainly has the following advantages that and effect:
(1) material powder that the present invention is prepared has preferable uniformity, dispersibility, and preparation process is simple, makes Make low in cost, experiment it is time-consuming it is shorter, environmental pollution is smaller, yield is higher, there is splendid industrial applications prospect.
(2) lithium ion battery negative material of the invention, first charge-discharge efficiency is high, and specific capacity height (reaches for the first time 900mAh/g, current commercialized graphite theoretical specific capacity are 372mAh/g), good cycle, effectively improve current lithium from The problem of sub- cell negative electrode material first charge discharge efficiency is low, low specific capacity.
It is another object of the present invention to provide a kind of preparation method of cathode material of lithium ion battery, including it is following Step:
The first step, by SbCl3It is dissolved in deionized water, obtains SbCl3Aqueous solution, ultrasound, stirring, is then added ethylene glycol, Continue ultrasound and stir, is then transferred to water heating kettle and carries out hydro-thermal reaction, to water heating kettle cooled to room temperature, by product utilization Deionized water and dehydrated alcohol centrifugation are alternately washed, dry, obtain black Sb2O3Powder；
Second step, the black Sb that the first step is obtained2O3Powder is placed in porcelain boat, by another porcelain boat equipped with thiocarbamide and is somebody's turn to do Equipped with black Sb2O3The porcelain boat of powder is put in tube furnace together, under inert gas protection, is sintered, and obtains trisulfides two The antimony oxide powder of antimony cladding.
A kind of improvement of preparation method as cathode material of lithium ion battery of the present invention, in the first step, the SbCl3 The concentration of aqueous solution is 2.5g/L-15g/L, ethylene glycol and SbCl3Mass ratio be 0.07-0.39.
A kind of improvement of preparation method as cathode material of lithium ion battery of the present invention, it is super for the first time in the first step The duration of sound is 3min-10min, and the duration of stirring is 20min-40min for the first time, second ultrasound it is lasting when Between be 3min-10min, the duration of second stirring is 20min-40min, and the duration of hydro-thermal reaction is 6h-18h, The temperature of hydro-thermal reaction is 140 DEG C -220 DEG C.
A kind of improvement of preparation method as cathode material of lithium ion battery of the present invention, in second step, Sb2O3Powder Mass ratio with thiocarbamide is 10:(1-10).
A kind of improvement of preparation method as cathode material of lithium ion battery of the present invention, in second step, sintering temperature It is 400 DEG C -900 DEG C, sintering duration 3h-9h, the heating rate of sintering is 3 DEG C/min-7 DEG C/min.
Specifically, obtaining Sb when sintering temperature is 400 DEG C -500 DEG C, sintering time is 3h-4.5h2S3Rodlike micro nanocrystalline Body particle；Sintering temperature is 450 DEG C -650 DEG C, and sintering time 4h-6h obtains Sb2S3Spherical micro-nano crystal grain；Sintering temperature Degree is 500 DEG C -700 DEG C, and sintering time 4.5h-7h obtains Sb2S3The micro-nano crystal grain of sea urchin shape；Sintering temperature be 600 DEG C- 800 DEG C, sintering time 5h-8h obtains Sb2S3The micro-nano crystal grain of cruciformity；Sintering temperature is 650 DEG C -900 DEG C, is burnt The knot time is 6h-9h, obtains Sb2S3Flower-shaped micro-nano crystal grain.
A kind of improvement of preparation method as cathode material of lithium ion battery of the present invention, stirring described in the first step are magnetic Power stirs, and inert gas described in second step is nitrogen or argon gas.
The present invention makes reactant SbCl by controlling different reaction conditions3Hydro-thermal, sintering generate antimonous sulfide cladding The negative electrode material of antimony oxide.First by SbCl3It is added in deionized water, ultrasonic 3-5min, stirs 20-30min, obtain white Color precipitates SbOCl, and ethylene glycol is added, can effective discrete particles, that is, ethylene glycol can serve as the effect of dispersing agent, can make to make The particle obtained has good dispersibility, continues ultrasound 3-5min, stirs 20-30min, white opacity liquid is obtained, by reactant It is transferred quickly to carry out hydro-thermal reaction in water heating kettle.In this reaction process, SbCl3It has been converted into Sb8O11Cl2And HCl, And Sb under hydrothermal conditions8O11Cl2It is more unstable, continue and water reacts, is converted into Sb2O3Particle namely SbCl3 Finally all it has been converted into Sb2O3。
And during the sintering process, thiocarbamide gradually thermally decomposes in protection atmosphere, causes the Sb in same atmosphere2O3 Slowly vulcanization occurs, obtains Sb2S3, and Sb2S3Particle has the structure trend of anisotropic growth, in specific sintering condition Under, Sb2S3Particle preferentially selects C axis to be grown, and obtains Sb2S3Nanorod structure.To by control sintering reaction when Between, the antimony oxide negative electrode material of the available antimonous sulfide cladding of the conditions such as temperature, the micro-nano powder being prepared Material not only has more regular pattern, and it with biggish specific surface area, there are also biggish draw ratios for some, in electrification , photoelectric field will have a good application prospect.
The hydro-thermal method has the characteristics that preparation process is simple, at low cost, experiment is time-consuming short, environmental-friendly, is suitble to current new The requirement of type green energy resource, has fabulous application prospect, and the vulcanization of part antimony oxide may be implemented in sintering process again.We Method is also expected to preparation and industrialization research applied to other type micro Nano materials.
It is another object of the present invention to provide a kind of lithium ion battery, including positive plate, negative electrode tab, be set to it is described Isolation film and electrolyte between positive plate and negative electrode tab, the negative electrode tab include negative current collector and are set to the cathode The cathode overlay of collection liquid surface, the cathode overlay include negative electrode active material, bonding agent and conductive agent, the cathode Active material is negative electrode material of the present invention.
Compared with the existing technology, lithium ion battery first charge-discharge efficiency of the invention is high, and specific capacity height (reaches for the first time 900mAh/g, current commercialized graphite theoretical specific capacity are 372mAh/g), good cycle, effectively improve current lithium from The problem of sub- cell negative electrode material first charge discharge efficiency is low, low specific capacity.
Detailed description of the invention
With reference to the accompanying drawings and detailed description, the present invention and its advantageous effects are described in detail.
Fig. 1 is the Sb for the Rod-like shape that embodiment 1 is prepared2S3Coat Sb2O3The SEM of micro-nano granules schemes.
Fig. 2 is the Sb for the Rod-like shape that embodiment 1 is prepared2S3Coat Sb2O3The XRD diagram of micro-nano granules.
Fig. 3 is the Sb for the spherical morphology that embodiment 2 is prepared2S3Coat Sb2O3The SEM of micro-nano granules schemes.
Fig. 4 is the Sb for the sea urchin shape pattern that embodiment 3 is prepared2S3Coat Sb2O3The SEM of micro-nano granules schemes.
Fig. 5 is the Sb for the cruciformity pattern that embodiment 4 is prepared2S3Coat Sb2O3The SEM of micro-nano granules schemes.
Fig. 6 is the Sb for the floriform appearance that embodiment 5 is prepared2S3Coat Sb2O3The SEM of micro-nano granules schemes.
The lithium ion battery negative material that Fig. 7 is embodiment 1, prepared by embodiment 2, embodiment 3, embodiment 4, embodiment 5 Charge-discharge performance figure.
The lithium ion battery negative material that Fig. 8 is embodiment 1, prepared by embodiment 2, embodiment 3, embodiment 4, embodiment 5 Charge-discharge magnification performance map.
Specific embodiment
Below the technical scheme of the invention is illustrated by a specific example, but the scope of the present invention is not limited thereto.
Embodiment 1
Present embodiments provide a kind of cathode material of lithium ion battery, negative electrode material has comprising stratum nucleare and shell Nucleocapsid structure；Stratum nucleare is antimony oxide, and shell is antimonous sulfide, and the mass ratio of stratum nucleare and shell is 1.43: 1, stratum nucleare Partial size is 100nm~2 μm, shell with a thickness of 50nm~0.5 μm, the micro-shape of stratum nucleare be it is rodlike, specific surface area is 217m2g-1。
Preparation method includes the following steps:
The first step, at room temperature, 0.25g SbCl3It is added in 30mL deionized water, ultrasonic 3min, magnetic force stirs 20min is mixed, 30mL ethylene glycol is added, ultrasonic 3min, magnetic agitation 20min are transferred in water heating kettle, 160 DEG C of heat preservation 10h, will Three times, revolving speed 6000r/min is put into 110 DEG C of vacuum drying ovens for product utilization deionized water and dehydrated alcohol alternating centrifugal, washing Middle dry 12h, obtains black Sb2O3Powder sample.
Second step, by black Sb2O3Powder sample is placed in porcelain boat and another porcelain boat equipped with 0.025g thiocarbamide is put jointly In tube furnace, it is passed through argon gas, the heating rate of 400 DEG C of sintering 4h, sintering are 5 DEG C/min, obtain corresponding black Sb2S3Packet Cover Sb2O3Powder.
By a small amount of Sb obtained2S3Coat Sb2O3Powder sample is directly adhered on the copper platform of conducting resinl, is carried out to it After metal spraying, observed under scanning electron microscope, as a result as shown in Figure 1.Sample is Rod-like shape, length 1- as can be observed from Figure 3 μm, width and height are 0.1-0.5 μm.
Fig. 2 is the Rod-like shape Sb of the present embodiment2S3Coat Sb2O3The X-ray powder diffraction pattern of powder sample.From figure It can be seen that Sb in spectrum2S3Coat Sb2O3The absorption peak position of sample and the Sb of rhombic form2S3It is (JCPDS, 42-1373) and vertical Prismatic crystal type Sb2O3(JCPDS, 43-1071) matches, and the sample illustrated is rhombic form Sb2S3Coat cubic Sb2O3 Material absorbs peak intensity and illustrates that sample has more perfect crystal structure more by force.Without finding other diffraction in diffracting spectrum Peak illustrates to prepare resulting sample with preferable purity.
Embodiment 2
Present embodiments provide a kind of cathode material of lithium ion battery, negative electrode material has comprising stratum nucleare and shell Nucleocapsid structure；Stratum nucleare is antimony oxide, and shell is antimonous sulfide, and the mass ratio of stratum nucleare and shell is 1.43: 1, stratum nucleare Partial size is 100nm~2 μm, shell with a thickness of 50nm~0.5 μm, the micro-shape of stratum nucleare be it is spherical, specific surface area is 370m2g-1。
Preparation method includes the following steps:
The first step, at room temperature, 0.25g SbCl3It is added in 30mL deionized water, ultrasonic 3min, magnetic force stirs 20min is mixed, 30mL ethylene glycol is added, ultrasonic 3min, magnetic agitation 20min are transferred in water heating kettle, 160 DEG C of heat preservation 10h, will Three times, revolving speed 6000r/min is put into 110 DEG C of vacuum drying ovens for product utilization deionized water and dehydrated alcohol alternating centrifugal, washing Middle dry 12h, obtains black Sb2O3Powder sample.
Second step, by black Sb2O3Powder sample is placed in porcelain boat and another porcelain boat equipped with 0.025g thiocarbamide is put jointly In tube furnace, it is passed through argon gas, the heating rate of 500 DEG C of sintering 5h, sintering are 4 DEG C/min, obtain corresponding black Sb2S3Packet Cover Sb2O3Powder.
By a small amount of Sb obtained2S3Coat Sb2O3Powder sample is directly adhered on the copper platform of conducting resinl, is carried out to it After metal spraying, observed under scanning electron microscope, as a result as shown in Figure 3.Sample is spherical morphology as can be observed from Figure, and diameter is 0.1μm。
Embodiment 3
Present embodiments provide a kind of cathode material of lithium ion battery, negative electrode material has comprising stratum nucleare and shell Nucleocapsid structure；Stratum nucleare is antimony oxide, and shell is antimonous sulfide, and the mass ratio of stratum nucleare and shell is 1.43: 1, stratum nucleare Partial size is 100nm~2 μm, shell with a thickness of 50nm~0.5 μm, the micro-shape of stratum nucleare is sea urchin shape, and specific surface area is 457m2g-1。
Preparation method includes the following steps:
The first step, at room temperature, 0.25g SbCl3It is added in 30mL deionized water, ultrasonic 3min, magnetic force stirs 20min is mixed, 30mL ethylene glycol is added, ultrasonic 3min, magnetic agitation 20min are transferred in water heating kettle, 160 DEG C of heat preservation 10h, will Three times, revolving speed 6000r/min is put into 110 DEG C of empty baking ovens for product utilization deionized water and dehydrated alcohol alternating centrifugal, washing Dry 12h, obtains black Sb2O3Powder sample.
Second step, by black Sb2O3Powder sample is placed in porcelain boat and another porcelain boat equipped with 0.025g thiocarbamide is put jointly In tube furnace, it is passed through argon gas, the heating rate of 600 DEG C of sintering 6h, sintering are 7 DEG C/min, obtain corresponding black Sb2S3Packet Cover Sb2O3Powder.
By a small amount of Sb obtained2S3Coat Sb2O3Powder sample is directly adhered on the copper platform of conducting resinl, is carried out to it After metal spraying, observed under scanning electron microscope, as a result as shown in Figure 4.Sample is sea urchin shape pattern, size as can be observed from Figure It is 15-30 μm.
Embodiment 4
Present embodiments provide a kind of cathode material of lithium ion battery, negative electrode material has comprising stratum nucleare and shell Nucleocapsid structure；Stratum nucleare is antimony oxide, and shell is antimonous sulfide, and the mass ratio of stratum nucleare and shell is 1.43: 1, stratum nucleare Partial size is 100nm~2 μm, shell with a thickness of 50nm~0.5 μm, the micro-shape of stratum nucleare is sea urchin shape, and specific surface area is 300m2g-1。
Preparation method includes the following steps:
The first step, at room temperature, 0.25g SbCl3It is added in 30mL deionized water, ultrasonic 3min, magnetic force stirs 20min is mixed, 30mL ethylene glycol is added, ultrasonic 3min, magnetic agitation 20min are transferred in water heating kettle, 160 DEG C of heat preservation 10h, will Three times, revolving speed 6000r/min is put into 110 DEG C of vacuum drying ovens for product utilization deionized water and dehydrated alcohol alternating centrifugal, washing Middle dry 12h, obtains black Sb2O3Powder sample；
Second step, by black Sb2O3Powder sample is placed in porcelain boat and another porcelain boat equipped with 0.025g thiocarbamide is put jointly In tube furnace, it is passed through argon gas, the heating rate of 700 DEG C of sintering 7h, sintering are 6 DEG C/min, obtain corresponding black Sb2S3Packet Cover Sb2O3Powder.
By a small amount of Sb obtained2S3Coat Sb2O3Powder sample is directly adhered on the copper platform of conducting resinl, is carried out to it After metal spraying, observed under scanning electron microscope, as a result as shown in Figure 5.Sample is cruciformity pattern, length as can be observed from Figure Degree is 10 μm, and width and height are 1-2 μm.
Embodiment 5
Present embodiments provide a kind of cathode material of lithium ion battery, negative electrode material has comprising stratum nucleare and shell Nucleocapsid structure；Stratum nucleare is antimony oxide, and shell is antimonous sulfide, and the mass ratio of stratum nucleare and shell is 1.43: 1, stratum nucleare Partial size is 100nm~2 μm, shell with a thickness of 50nm~0.5 μm, the micro-shape of stratum nucleare is sea urchin shape, and specific surface area is 420m2g-1。
Preparation method includes the following steps:
The first step, at room temperature, 0.25g SbCl3It is added in 30mL deionized water, ultrasonic 3min, magnetic force stirs 20min is mixed, 30mL ethylene glycol is added, is centrifuged 3min, magnetic agitation 20min is transferred in water heating kettle, 160 DEG C of heat preservation 10h, will Three times, revolving speed 6000r/min is put into 110 DEG C of vacuum drying ovens for product utilization deionized water and dehydrated alcohol alternating centrifugal, washing Middle dry 12h, obtains black Sb2O3Powder sample.
Second step, by black Sb2O3Powder sample is placed in porcelain boat and another porcelain boat equipped with 0.025g thiocarbamide is put jointly In tube furnace, it is passed through argon gas, the heating rate of 400 DEG C of sintering 4h, sintering are 3 DEG C/min, obtain corresponding black Sb2S3@ Sb2O3Powder.
By a small amount of Sb obtained2S3Coat Sb2O3Powder sample is directly adhered on the copper platform of conducting resinl, to it After carrying out metal spraying, observed under scanning electron microscope, as a result as shown in Figure 6.Sample is floriform appearance, length as can be observed from Figure Degree is 10 μm, and width and height are 0.1-0.2 μm.
Embodiment 6
Present embodiments provide a kind of cathode material of lithium ion battery, negative electrode material has comprising stratum nucleare and shell Nucleocapsid structure；Stratum nucleare is antimony oxide, and shell is antimonous sulfide, and the mass ratio of stratum nucleare and shell is 3.43: 1, stratum nucleare Partial size is 100nm~2 μm, shell with a thickness of 50nm~0.5 μm, the micro-shape of stratum nucleare be it is rodlike, specific surface area is 200m2g-1。
Preparation method includes the following steps:
The first step, by SbCl3It is dissolved in deionized water, obtains the SbCl that concentration is 3.3g/L3Aqueous solution, ultrasonic 5min, magnetic Power stirs 30min, 30mL ethylene glycol is then added, so that ethylene glycol and SbCl3Mass ratio be 0.294:1, continue ultrasound 5min and magnetic agitation 30min are then transferred to water heating kettle and carry out hydro-thermal reaction, and the duration of hydro-thermal reaction is 12h, hydro-thermal The temperature of reaction is 180 DEG C, to water heating kettle cooled to room temperature, by product utilization deionized water and dehydrated alcohol centrifugation, is handed over It is dry for washing, obtain black Sb2O3Powder；
Second step, the black Sb that the first step is obtained2O3Powder is placed in porcelain boat, by another porcelain boat equipped with 0.01g thiocarbamide Black Sb is housed with this2O3The porcelain boat of powder is put in tube furnace together, wherein Sb2O3The mass ratio of powder and thiocarbamide is 6:1, Under nitrogen protection, it being sintered, sintering temperature is 800 DEG C, sintering duration 8h, the heating rate of sintering is 7 DEG C/ min.Obtain the antimony oxide powder of antimonous sulfide cladding.
Embodiment 7
Present embodiments provide a kind of cathode material of lithium ion battery, negative electrode material has comprising stratum nucleare and shell Nucleocapsid structure；Stratum nucleare is antimony oxide, and shell is antimonous sulfide, and the mass ratio of stratum nucleare and shell is 3.43:1, stratum nucleare Partial size is 100nm~2 μm, shell with a thickness of 50nm~0.5 μm, the micro-shape of stratum nucleare be it is rodlike, specific surface area is 205m2g-1。
Preparation method includes the following steps:
The first step, by SbCl3It is dissolved in deionized water, obtains the SbCl that concentration is 3.3g/L3Aqueous solution, ultrasonic 7min, magnetic Power stirs 35min, ethylene glycol is then added, so that glycol and SbCl3Mass ratio be 0.294:1, continue ultrasound 7min simultaneously Magnetic agitation 35min is then transferred to water heating kettle and carries out hydro-thermal reaction, and the duration of hydro-thermal reaction is 8h, hydro-thermal reaction Temperature is 200 DEG C, and to water heating kettle cooled to room temperature, product utilization deionized water and dehydrated alcohol centrifugation, alternating are washed, It is dry, obtain black Sb2O3Powder；
Second step, the black Sb that the first step is obtained2O3Powder is placed in porcelain boat, by another porcelain boat equipped with 0.01g thiocarbamide Black Sb is housed with this2O3The porcelain boat of powder is put in tube furnace together, wherein Sb2O3The mass ratio of powder and thiocarbamide is 6:1, Under nitrogen protection, it being sintered, sintering temperature is 500 DEG C, sintering duration 5h, the heating rate of sintering is 5 DEG C/ min.Obtain the antimony oxide powder of antimonous sulfide cladding.
Embodiment 8
Present embodiments provide a kind of cathode material of lithium ion battery, negative electrode material has comprising stratum nucleare and shell Nucleocapsid structure；Stratum nucleare is antimony oxide, and shell is antimonous sulfide, and the mass ratio of stratum nucleare and shell is 0.86: 1, stratum nucleare Partial size is 100nm~2 μm, shell with a thickness of 50nm~0.5 μm, the micro-shape of stratum nucleare be it is rodlike, specific surface area is 220m2g-1。
Preparation method includes the following steps:
The first step, by SbCl3It is dissolved in deionized water, obtains the SbCl that concentration is 6.6g/L3Aqueous solution, ultrasonic 4min, magnetic Power stirs 25min, ethylene glycol is then added, so that ethylene glycol and SbCl3Mass ratio be 0.147:1, continue ultrasound 4min And magnetic agitation 25min, it is then transferred to water heating kettle and carries out hydro-thermal reaction, the duration of hydro-thermal reaction is 14h, hydro-thermal reaction Temperature be 150 DEG C, to water heating kettle cooled to room temperature, by product utilization deionized water and dehydrated alcohol centrifugation, alternately wash It washs, it is dry, obtain black Sb2O3Powder；
Second step, the black Sb that the first step is obtained2O3Powder is placed in porcelain boat, by another porcelain equipped with 0.005g thiocarbamide Boat is equipped with black Sb with this2O3The porcelain boat of powder is put in tube furnace together, wherein Sb2O3The mass ratio of powder and thiocarbamide is 2.56:1 is sintered under nitrogen protection, and sintering temperature is 550 DEG C, sintering duration 7h, the heating rate of sintering For 6 DEG C/min.Obtain the antimony oxide powder of antimonous sulfide cladding.
Embodiment 9
Present embodiments provide a kind of cathode material of lithium ion battery, negative electrode material has comprising stratum nucleare and shell Nucleocapsid structure；Stratum nucleare is antimony oxide, and shell is antimonous sulfide, and the mass ratio of stratum nucleare and shell is 0.86: 1, stratum nucleare Partial size is 100nm~2 μm, shell with a thickness of 50nm~0.5 μm, the micro-shape of stratum nucleare be it is rodlike, specific surface area is 235m2g-1。
Preparation method includes the following steps:
The first step, by SbCl3It is dissolved in deionized water, obtains the SbCl that concentration is 6.6g/L3Aqueous solution, ultrasonic 8min, magnetic Power stirs 28min, ethylene glycol is then added, so that ethylene glycol and SbCl3Mass ratio be 0.147:1, continue ultrasound 6min And magnetic agitation 22min, it is then transferred to water heating kettle and carries out hydro-thermal reaction, the duration of hydro-thermal reaction is 9h, hydro-thermal reaction Temperature be 170 DEG C, to water heating kettle cooled to room temperature, by product utilization deionized water and dehydrated alcohol centrifugation, alternately wash It washs, it is dry, obtain black Sb2O3Powder；
Second step, the black Sb that the first step is obtained2O3Powder is placed in porcelain boat, by another porcelain boat equipped with 0.05g thiocarbamide Black Sb is housed with this2O3The porcelain boat of powder is put in tube furnace together, wherein Sb2O3The mass ratio of powder and thiocarbamide is 2.56:1 is sintered under nitrogen protection, and sintering temperature is 750 DEG C, sintering duration 7.5h, the heating speed of sintering Rate is 4.5 DEG C/min.Obtain the antimony oxide powder of antimonous sulfide cladding.
Embodiment 10
Present embodiments provide a kind of lithium ion battery, including positive plate, negative electrode tab, be set to positive plate and negative electrode tab it Between isolation film and electrolyte, negative electrode tab includes negative current collector and the cathode overlay for being set to negative current collector surface, Cathode overlay includes negative electrode active material, bonding agent and conductive agent, and negative electrode active material is the negative electrode material of embodiment 1.
In the present embodiment, negative electrode active material is the Sb of embodiment 12S3Micro-nano powder, conductive agent are preferably acetylene black, Binder is preferably Kynoar.Sb2S3The mass ratio of micro-nano powder, conductive agent and binder is (75-80): (15- 10): 10, specifically, being 80:10:10 in the present embodiment, progress is dry-mixed, and after appropriate NMP is added, wet mixing is coated with after mixing evenly On a current collector, coating thickness is 60-110 microns, and the present embodiment is 110 microns, in 80-110 DEG C of vacuum drying 10-12h, then The pole piece that diameter is 12-14mm is made.For in 100 DEG C of vacuum drying 11h in the present embodiment, then the cathode that diameter is 12mm is made Piece.
Then the round pole piece for using sheet-punching machine that negative electrode tab is washed into diameter as 12mm is pour lithium slice, electrolyte to electrode For 1mol/L LiPF6Solution (solvent is that ethylene carbonate EC+ dimethyl carbonate DMC is formulated according to mass ratio 1:1), every Film is microporous polypropylene membrane Celgard-2300, and assembly obtains CR2032 type button cell C1 in the glove box full of argon gas.
Embodiment 11-18
As different from Example 10, negative electrode active material is the Sb of embodiment 2-92S3Micro-nano powder, remaining is the same as implementation Example 10, which is not described herein again, and it is C2-C9 that obtained button cell is numbered respectively.
Battery C1-C9 is tested for the property, tests the charge and discharge of battery C1-C9 respectively using LAND battery test system Specific capacity cycle performance, wherein carry out the experiment of constant current charge-discharge specific capacity loop test with the electric current of 0.1C=94.6mA/g, fill Discharge voltage is limited in 0.005-2.5V.
Battery C1-C9 is tested for the property, tests the charge and discharge of battery C1-C9 respectively using LAND battery test system Specific capacity high rate performance, wherein carry out constant current charge and discharge with the electric current of 0.1C (94.6mA/g), 0.25C, 0.5C, 1C, 1.5C, 2C Electric specific capacity multiplying power test experiments, charging/discharging voltage are limited in 0.005-2.5V.
Test result is as follows:
Fig. 7 is the one-dimensional and its compound pattern Sb that different embodiments obtain2S3Coat Sb2O3Micro-nano powder material follows Ring Capacity Plan.It can be seen from the figure that rodlike Sb2S3Coat Sb2O3Micro-nano powder have more excellent cyclical stability and Preferable capacity retention ratio recycles under the electric current of 0.1C (94.6mAh/g), the capacity of first charge-discharge close to 900mAh/g, After 80 circle of circulation, capacity is still stably held in 300mAh/g, has more excellent property as lithium ion battery negative material Energy.
Fig. 8 is the one-dimensional and its compound pattern Sb that different embodiments obtain2S3Coat Sb2O3Times of micro-nano powder material Rate Capacity Plan.It can be seen from the figure that rodlike Sb2S3Coat Sb2O3Micro-nano powder have more excellent high rate performance and compared with Good capacity retention ratio, recycles under the electric current of 0.1C (94.6mAh/g), and the capacity of first charge-discharge is passed through close to 900mAh/g The circulation of larger multiplying power is crossed, capacity still can be stably held in 600mAh/g or so after 30 circles, as negative electrode of lithium ion battery Material has more excellent performance.
1 is shown in Table to the performance test results of battery C1-C9:
Table 1: the performance test results of battery C1-C9
As can be seen from Table 1: using negative electrode material of the invention lithium ion battery specific capacity for the first time with higher, compared with Good cycle performance and high rate performance.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula is changed and is modified.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to of the invention Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although being used in this specification Some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.

Claims (8)

1. a kind of cathode material of lithium ion battery, which is characterized in that the negative electrode material has the core-comprising stratum nucleare and shell Shell structure；
The stratum nucleare is antimony oxide, and the shell is antimonous sulfide, and the mass ratio of the stratum nucleare and the shell is (0.4-5):1；
The partial size of the stratum nucleare be 100nm~2 μm, the shell with a thickness of 50nm~0.5 μm.
2. cathode material of lithium ion battery according to claim 1, it is characterised in that: the specific surface of the negative electrode material Product is 200-500m2g-1, the micro-shape of the stratum nucleare is rodlike, spherical, sea urchin shape, cruciformity or flower-shaped.
3. a kind of preparation method of the described in any item cathode material of lithium ion battery of claim 1 to 2, which is characterized in that The following steps are included:
The first step, by SbCl3It is dissolved in deionized water, obtains SbCl3Aqueous solution, ultrasound, stirring, is then added ethylene glycol, continues Ultrasound simultaneously stirs, and is then transferred to water heating kettle and carries out hydro-thermal reaction, to water heating kettle cooled to room temperature, by product utilization go from Sub- water and dehydrated alcohol centrifugation are alternately washed, dry, obtain black Sb2O3Powder；
Second step, the black Sb that the first step is obtained2O3Powder is placed in porcelain boat, and another porcelain boat equipped with thiocarbamide is equipped with this Black Sb2O3The porcelain boat of powder is put in tube furnace together, under protective gas protection, is sintered, is obtained antimonous sulfide The antimony oxide powder of cladding；
In second step, sintering temperature is 400 DEG C -900 DEG C, sintering duration 3h-9h, the heating rate of sintering is 3 DEG C/ min-7℃/min。
4. the preparation method of cathode material of lithium ion battery according to claim 3, it is characterised in that: in the first step, The SbCl3The concentration of aqueous solution is 2.5g/L-15g/L, ethylene glycol and SbCl3Mass ratio be 0.07-0.39.
5. the preparation method of cathode material of lithium ion battery according to claim 3, it is characterised in that: in the first step, The duration of ultrasound is 3min-10min for the first time, and the duration of stirring is 20min-40min, second of ultrasound for the first time Duration be 3min-10min, the duration of second stirring is 20min-40min, and the duration of hydro-thermal reaction is 6h-18h, the temperature of hydro-thermal reaction are 140 DEG C -220 DEG C.
6. the preparation method of cathode material of lithium ion battery according to claim 3, it is characterised in that: in second step, Sb2O3The mass ratio of powder and thiocarbamide is 10:(1-10).
7. the preparation method of cathode material of lithium ion battery according to claim 3, it is characterised in that: described in the first step Stirring is magnetic agitation, and protective gas described in second step is nitrogen or argon gas.
8. a kind of lithium ion battery, including positive plate, negative electrode tab, the isolation film that is set between the positive plate and negative electrode tab with And electrolyte, the negative electrode tab include negative current collector and the cathode overlay for being set to the negative current collector surface, it is described Cathode overlay includes negative electrode active material, bonding agent and conductive agent, it is characterised in that: the negative electrode active material is wanted for right Seek 1 to 2 described in any item negative electrode materials.
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