CN103972497B - Lithium ion battery Co2snO4/ C nano composite negative pole material and preparation and application thereof - Google Patents
Lithium ion battery Co2snO4/ C nano composite negative pole material and preparation and application thereof Download PDFInfo
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- H01M4/00—Electrodes
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- H—ELECTRICITY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- H—ELECTRICITY
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Abstract
The invention discloses a kind of lithium ion battery Co2SnO4/ C nano composite negative pole material and preparation and application thereof.Said method comprising the steps of: pink salt and cobalt salt are dissolved in dispersant and obtain dispersion liquid, then drip sodium hydroxide solution under conditions of stirring in dispersion liquid, reaction is filtered or is centrifuged, vacuum drying obtains powder；React after powder being placed under inert gas environment and being warming up to 900 DEG C, obtain product, then product and graphite are carried out the mechanical ball milling of a period of time, nano ball grinding again, the solution centrifugal obtained finally takes precipitation, and washing is dried, obtains described lithium ion battery Co2SnO4/ C nano composite negative pole material.The lithium ion battery Co that the present invention prepares2SnO4/ C nano composite negative pole material uses the form being doped with amorphous carbon, and first charge-discharge efficiency is high, and specific capacity is high, good cycling stability.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of lithium ion battery Co2SnO4/ C nano composite negative pole material and preparation and application thereof.
Background technology
Lithium ion battery, owing to having the advantages such as voltage height, memory-less effect, energy density be big, pollution-free, has been widely used in the mobile devices such as mobile phone, digital camera, notebook computer now.Due to development and the demand of the energy of science and technology, lithium ion battery was progressively applied to electric bicycle and and the field such as hybrid-power electric vehicle in the last few years.At present commercial li-ion cell negative electrode material mainly uses material with carbon element, but the specific capacity that material with carbon element is relatively low (372mAh g-1) limit its application in high-power power lithium battery direction.Bigger in order to develop energy density, the higher lithium cell negative pole material of specific capacity, people have been increasingly turned to transition-metals and their oxides material goal in research.In crossing metal oxide materials, there is the Sn atom spinelle arranged side by side with O atom or inverse spinel structure ternary tin sill, M2SnO4, the specific capacity higher due to it is of great interest.The system that ternary tin sill is studied at present mainly has Mg2SnO4、Co2SnO4、Mn2SnO4、Zn2SnO4Deng.Wherein, Co2SnO4Material is owing to having 1088mAh g-1Theoretical specific capacity (three times of graphite specific capacity), and receive much concern in numerous ternary alloy three-partalloys.But, Co2SnO4Material is susceptible to stepwise reaction during long circulating and generates SnO2, and lithium ion embedding de-during cubical expansivity too high, cause the mechanical disintegration of active substance, cause electrode avalanche efflorescence inefficacy, electrode cycle hydraulic performance decline, and then affect the cycle performance of battery, limit its business-like application.
At present, Co2SnO4Preparation method mainly have hydro-thermal method and a coprecipitation, but Co prepared by two kinds of methods2SnO4All there is the shortcoming that capacity attenuation is too fast in negative material, it is impossible to adapts to the requirement of lithium-ion-power cell.Wang Gang hydro-thermal method prepares the spinel-type cobaltous stannate granule about size 100nm, and its capacity i.e. decayed more than 50% at 50 weeks；Being coated with one layer of amorphous carbon by hydro-thermal method in cobaltous stannate particle surface Qi Yue, its capacity was only capable of at 75 weeks maintaining 474mAh g-1.Further, it is little that hydro-thermal method also has yield, the shortcoming of response time length, it is impossible to carries out industrial applications.To this end, the thinking that people are by mixture ball milling, introduce other constituent elements, utilize polynary or heterogeneous effect, improve the charge and discharge circulation life of electrode material.Research shows, transition metal oxide and material with carbon element are carried out ball milling doping, pure crystalline structure is decomposed into amorphous state and crystalline state mixed structure, can alleviate bulk effect big in charge and discharge process；Utilize material with carbon element cyclical stability height, the feature of good conductivity, cycle performance and the high rate performance of battery can be effectively improved.
Summary of the invention
In place of shortcoming and defect for solution prior art, the primary and foremost purpose of the present invention is to provide a kind of lithium ion battery Co2SnO4The preparation method of/C nano composite negative pole material.
Another object of the present invention is to the lithium ion battery Co providing above-mentioned preparation method to obtain2SnO4/ C nano composite negative pole material.
It is still another object of the present invention to provide the lithium ion battery Co that above-mentioned preparation method obtains2SnO4The application of/C nano composite negative pole material.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of lithium ion battery Co2SnO4The preparation method of/C nano composite negative pole material, comprises the following steps:
(1) pink salt and cobalt salt are dissolved in dispersant obtain dispersion liquid, then stirring under conditions of in dispersion liquid with 5～15mL/min speed drip sodium hydroxide solution, stirring reaction 10～20min after dripping, filters or centrifuging and taking precipitation, precipitation vacuum drying is obtained powder；
(2) react 6～12h after being placed under inert gas environment and be warming up to 900～950 DEG C by the powder that step (1) obtains, obtain product, then by product and graphite mechanical ball milling 12～48h；
(3) the product nano ball milling 8～24h obtained by step (2) mechanical ball milling, then takes precipitation by the solution centrifugal obtained, then by washing of precipitate, be dried, obtain described lithium ion battery Co2SnO4/ C nano composite negative pole material.
Preferably, the pink salt described in step (1) is solubility pink salt, and described cobalt salt is soluble cobalt, and described dispersant is deionized water；In described dispersion liquid, tin ion is 1:2 with the mol ratio of cobalt ion.
It is furthermore preferred that described solubility pink salt is the one in stannic chloride, nitric acid stannum or STANNOUS SULPHATE CRYSTALLINE；Described soluble cobalt is the one in cobaltous chloride, cobalt nitrate or cobaltous sulfate.
Preferably, in the reactant liquor after dripping sodium hydroxide solution in step (1), the concentration of sodium hydroxide is 2mol/L；Described vacuum drying temperature is 60～90 DEG C, and the vacuum drying time is 8～12h；Described mixing speed is 100～500r/min.
Preferably, noble gas described in step (2) is nitrogen or the argon of purity 99.999% of purity 99.999%；Described programming rate is 2～5 DEG C/min；Described graphite is native graphite, electrographite or modified graphite.
Preferably, step (2) adds, before product and graphite ball milling, the zirconia ball that particle diameter is 3～10mm；Wherein product is (3:7)～(7:3) with the mass ratio of graphite；The mixture of product and graphite and the mass ratio of zirconia ball are (70～75): 1, and mechanical ball milling rotating speed is 300～350r/s.
Preferably, described in step (3), nano ball grinding rotating speed is 3500～3800r/min；Described washing is that dehydrated alcohol and deionized water alternately rinse several times；Described baking temperature is 60 DEG C, and drying time is 8h.
The lithium ion battery Co that above-mentioned preparation method obtains2SnO4/ C nano composite negative pole material.
The lithium ion battery Co that above-mentioned preparation method obtains2SnO4The application in the preparing anode plate for lithium ionic cell of/C nano composite negative pole material, comprises the steps:
By lithium ion battery Co2SnO4/ C nano composite negative pole material, binding agent and conductive agent press (75～85): (15～5): be coated on Copper Foil after the mass ratio mixing of 10, carry out roll-in, obtain anode plate for lithium ionic cell after 50～100 DEG C of vacuum drying 5～24h.
Preferably, described binding agent is binding agent LA132 or polyvinylidene fluoride；Described conductive agent is conductive carbon black or nano-sized carbon；
Described lithium ion battery Co2SnO4The mass ratio of/C nano composite negative pole material, binding agent and conductive agent is 75:15:10；
Described coating thickness is 100～180 microns；Roll-in thickness is 75～150 microns.
Described binding agent LA132 is the aqueous binders that Chengdu Yindile Power Source Science and Technology Co., Ltd produces.Described nano-sized carbon particle diameter is 10～100nm.
The cobaltous stannate that coprecipitation is prepared by the present invention and graphite carry out mechanical ball milling, can effectively reduce the particle diameter of large scale graphite, thus the attachment and follow-up nano ball grinding for cobaltous stannate granule is prepared.In nano ball grinding operation, the cobaltous stannate granule of 60～about 80nm mutually extrudes with flaky graphite and crushes, and forms cobaltous stannate/graphite composite structure that amorphous state mixes with crystalline state.This structure can effectively alleviate Volumetric expansion big in material charge and discharge process, and improves the electric conductivity of material, improves the cycle performance of material.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) present invention is by pure Co2SnO4With the nano ball grinding that the graphite after pulverizing carries out 6～24 hours, after graphite ball milling, randomness strengthens, and the amorphous carbon of formation improves the cyclical stability of material, and effectively alleviates Volumetric expansion, and then improve the performance of material, effectively raises Co2SnO4The specific capacity of/C nano composite negative pole material, electrical conductivity and cycle performance.
(2) the lithium ion battery Co that the present invention prepares2SnO4/ C nano composite negative pole material uses the form being doped with graphite, Co2SnO4/ C composite negative pole material has good cyclical stability and high rate performance, compared to pure Co2SnO4Material, its first charge-discharge efficiency is high, and specific capacity is high, and (within 100 weeks, capacity is maintained at 550mAh g-1Recycle ratio capacity), good cycling stability, successfully solve Co2SnO4The irreversible capacity loss that material exists when being applied to lithium ion battery negative is big, recycle ratio capacity attenuation is fast and the problem of poorly conductive.
(3) present invention utilizes coprecipitation to prepare cobaltous stannate, compared to traditional hydro-thermal method and solid-state high-temperature decomposition, has the advantage that yield is big, the response time is short and saves the energy；And graphite material is with low cost needed for ball milling, it is easy to obtain, advantageously in the industrialized production of material.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of product in embodiment 1 step (2).
Fig. 2 is the SEM pattern of product in embodiment 1 step (2).
Fig. 3 is the lithium ion battery Co of embodiment 1 preparation2SnO4The SEM pattern of/C nano composite negative pole material.
Fig. 4 is the lithium ion battery Co of embodiment 2 preparation2SnO4The SEM pattern of/C nano composite negative pole material.
Fig. 5 is the lithium ion battery Co of embodiment 3 preparation2SnO4The SEM pattern of/C nano composite negative pole material.
Fig. 6 is the lithium ion battery Co of embodiment 4 preparation2SnO4The CV curve of/C nano composite negative pole material.
Fig. 7 is the charge-discharge performance figure of simulated battery 1.
Fig. 8 is the charge-discharge performance figure of simulated battery 2.
Fig. 9 is the charge-discharge performance figure of simulated battery 3.
Figure 10 is the charge-discharge performance figure of simulated battery 4.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
In the embodiment of the present invention, native graphite, electrographite and modified graphite are purchased from Shenzhen City Beiterui New Energy Materials Co., Ltd；Conductive carbon black is conductive carbon Super-P that Shenzhen City Beiterui New Energy Materials Co., Ltd produces.
Embodiment 1
Prepare anode plate for lithium ionic cell, specifically comprise the following steps that
(1) lithium ion battery Co is prepared2SnO4/ C nano composite negative pole material:
(1) 0.875g five hydrous tin chloride and 1.19g cobalt chloride hexahydrate are dissolved in 50mL deionized water obtain dispersion liquid, then under conditions of stirring, (100r/min) drips 50mL sodium hydroxide solution with the speed of 5mL/min in dispersion liquid, it is ensured that dripping the concentration of NaOH in rear solution is 2mol/L.Continue stirring reaction 10min after dripping, then reactant liquor centrifuging and taking is precipitated, gained is precipitated 60 DEG C of vacuum drying 12h and obtains powder；Wherein, in dispersion liquid, the molar concentration of tin ion is 0.05mol/L, and the molar concentration of cobalt ion is 0.1mol/L, and tin ion is 1:2 with the mol ratio of cobalt ion；
(2) powder that step (1) obtains is placed in Muffle furnace, reacts 6h after being passed through noble gas in Muffle furnace and being warming up to 900 DEG C with 2 DEG C/min, obtain product；Then 0.75g product and 1.75g graphite being put into ball milling 24h in planetary type ball-milling tank, add 175g zirconia ball before ball milling, the mixture quality of zirconia ball and graphite and cobaltous stannate ratio is for 70:1；Described noble gas is the nitrogen of purity 99.999%；Described graphite is native graphite；Ball milling speed is 330r/s；
(3) product that step (2) ball milling obtains is put in nanon ball-mill with 3500r/min ball milling 8h, then the solution centrifugal obtained is taken precipitation, again precipitation dehydrated alcohol and deionized water are alternately rinsed 5 times, last 60 DEG C of dry 8h, obtain described lithium ion battery Co2SnO4/ C nano composite negative pole material.
The product that step (2) obtains carries out XRD figure spectrum detection, and testing result is as it is shown in figure 1, this collection of illustrative plates three strongest ones peak and Co2SnO4Standard card JCPDS:29-0514 matches, and illustrates that step (2) products therefrom is pure Co2SnO4。
Product Co that step (2) is obtained2SnO4Lithium ion battery Co with final gained2SnO4/ C nano composite negative pole material carries out SEM morphology characterization, the most as shown in Figure 2 and Figure 3.The purest cobaltous stannate is to be connected with each other by the nano-particle of granularity about about 100nm to form, and ball milling afterproduct is flakey, tiny Co2SnO4Embed in graphite, form Co2SnO4/ C nano composite negative pole material.
(2) the lithium ion battery Co that 2g step () is obtained2SnO4/ C nano composite negative pole material uniformly mixes with binding agent LA132 (agglomerant concentration is 0.033g/mL), conductive carbon Super-P of 0.267g of 12.03g, furnishing slurry, it is coated on Copper Foil, coating thickness is 100 microns, and is prepared as anode plate for lithium ionic cell 1 through 100 DEG C of vacuum drying 6 hours, roll-in (thickness is 85 microns).
Embodiment 2
Prepare anode plate for lithium ionic cell, specifically comprise the following steps that
(1) lithium ion battery Co is prepared2SnO4/ C nano composite negative pole material:
(1) 0.875g five hydrous tin chloride and 1.19g cobalt chloride hexahydrate are dissolved in 50mL deionized water obtain dispersion liquid, then under conditions of stirring, (250r/min) drips 50mL sodium hydroxide solution with the speed of 10mL/min in dispersion liquid, it is ensured that dripping the concentration of NaOH in rear solution is 2mol/L.Continue stirring reaction 10min after dripping, then reactant liquor centrifuging and taking is precipitated, precipitation 70 DEG C vacuum drying 10h is obtained powder；Wherein, in dispersion liquid, the molar concentration of tin ion is 0.05mol/L, and the molar concentration of cobalt ion is 0.1mol/L, and tin ion is 1:2 with the mol ratio of cobalt ion；
(2) powder that step (1) obtains is placed in Muffle furnace, reacts 9h after being passed through noble gas in Muffle furnace and being warming up to 950 DEG C with 3 DEG C/min, obtain product；Then 0.75g product and 0.75g graphite being put into ball milling 30h in planetary type ball-milling tank, add 108g zirconia ball before ball milling, the mixture quality of zirconia ball and graphite and cobaltous stannate ratio is for 72:1；Described noble gas is the argon of purity 99.999%；Described graphite is electrographite；Ball milling speed is 300r/s；
(3) product that step (2) ball milling obtains is put in nanon ball-mill with 3650r/min ball milling 16h, then the solution centrifugal obtained is taken precipitation, again precipitation dehydrated alcohol and deionized water are alternately rinsed 5 times, last 60 DEG C of dry 8h, obtain described lithium ion battery Co2SnO4/ C nano composite negative pole material.
By the lithium ion battery Co of final gained2SnO4/ C nano composite negative pole material carries out SEM morphology characterization, as shown in Figure 4.As can be seen from the figure sample topography is flakey, tiny Co2SnO4Embed in graphite, form Co2SnO4/ C composite, flaky graphite is evenly distributed, this cycle performance being conducive to improving material.
(2) the lithium ion battery Co that 1g step () is obtained2SnO4/ C nano composite negative pole material uniformly mixes with binding agent LA132 (agglomerant concentration is 0.033g/mL), conductive carbon Super-P of 0.134g of 6.02g, furnishing slurry, it is coated on Copper Foil, coating thickness is 100 microns, and is prepared as anode plate for lithium ionic cell 2 through 100 DEG C of vacuum drying 6 hours, roll-in (thickness is 85 microns).
Embodiment 3
Prepare anode plate for lithium ionic cell, specifically comprise the following steps that
(1) lithium ion battery Co is prepared2SnO4/ C nano composite negative pole material:
(1) 0.875g five hydrous tin chloride and 1.19g cobalt chloride hexahydrate are dissolved in 50mL deionized water obtain dispersion liquid, then under conditions of stirring, (500r/min) drips 50mL sodium hydroxide solution with the speed of 15mL/min in dispersion liquid, it is ensured that dripping the concentration of NaOH in rear solution is 2mol/L.Continue stirring reaction 10min after dripping, then reactant liquor centrifuging and taking is precipitated, precipitation 90 DEG C vacuum drying 8h is obtained powder；Wherein, in dispersion liquid, the molar concentration of tin ion is 0.05mol/L, and the molar concentration of cobalt ion is 0.1mol/L, and tin ion is 1:2 with the mol ratio of cobalt ion；
(2) powder that step (1) obtains is placed in Muffle furnace, reacts 12h after being passed through noble gas in Muffle furnace and being warming up to 900 DEG C with 5 DEG C/min, obtain product；Then 0.75g product and 0.32g graphite being put into ball milling 36h in planetary type ball-milling tank, add 80.5g zirconia ball before ball milling, the mixture quality of zirconia ball and graphite and cobaltous stannate ratio is for 75:1；Described noble gas is the nitrogen of purity 99.999%；Described graphite is modified graphite；Ball milling speed is 350r/s；
(3) product that step (2) ball milling obtains is put in nanon ball-mill with 3800r/min ball milling 24h, then the solution centrifugal obtained is taken precipitation, again precipitation dehydrated alcohol and deionized water are alternately rinsed 5 times, last 60 DEG C of dry 8h, obtain described lithium ion battery Co2SnO4/ C nano composite negative pole material.
By the lithium ion battery Co of final gained2SnO4/ C nano composite negative pole material carries out SEM morphology characterization, as shown in Figure 5.As can be seen from the figure sample topography is bulk, but still it can be seen that flaky graphite, tiny Co inside blocky-shaped particle2SnO4Uniformly mix with flaky graphite, favourable to the chemical property of material.
(2) the lithium ion battery Co that 1g step () is obtained2SnO4/ C nano composite negative pole material uniformly mixes with binding agent LA132 (agglomerant concentration is 0.033g/mL), conductive carbon Super-P of 0.134g of 6.02g, furnishing slurry, it is coated on Copper Foil, coating thickness is 100 microns, and is prepared as anode plate for lithium ionic cell 3 through 100 DEG C of vacuum drying 6 hours, roll-in (thickness is 85 microns).
Comparative example 1
Prepare anode plate for lithium ionic cell, specifically comprise the following steps that
(1) lithium ion battery Co is prepared2SnO4Nano composite anode material:
(1) 0.875g five hydrous tin chloride and 1.19g cobalt chloride hexahydrate are dissolved in 50ml water dispersion and obtain dispersion liquid；Wherein, in dispersion liquid, the molar concentration of tin ion is 0.05mol/L, and the molar concentration of cobalt salt is 0.1mol/L, and tin ion is 1:2 with the mol ratio of cobalt ion；
(2) NaOH solution 50ml of 4mol/L is configured, in the case of the magnetic agitation of 500r/min, the NaOH solution configured is added dropwise in step (1) gained dispersion liquid, after continuing stirring 10min, the navy blue mixed solution obtained is centrifuged, and in 80 DEG C of vacuum drying ovens, dry 10h, obtain blue powder；
(3) powder sample taking step (2) is placed in Muffle furnace, reacts 8h, obtain product in Muffle furnace after being passed through noble gas and being warming up to 900 DEG C with 5 DEG C/min；
(4) taking the product 0.75g that step (3) obtains and put in planetary type ball-milling tank, add 56.5g zirconia ball before ball milling, zirconia ball and mixture quality ratio is for 75:1, ball milling 30h；
(5) take the product after the ball milling that step (4) obtains to put in nanon ball-mill with 3700r/min ball milling 16h, the solution centrifugal obtained is filtered black precipitate, alternately rinse 5 times with dehydrated alcohol and water respectively, 60 DEG C of dry 8h, obtain lithium ion battery Co2SnO4Nano composite anode material.
Final gained sample is carried out CV test, and test result is as shown in Figure 6.Can be seen that sample oxidation peak disappears the most substantially, and CV first week is bigger with difference two weeks after.The cobaltous stannate that individually ball milling is pure will cause the pulverizing of cobaltous stannate crystalline particles and rupture, and causes the excess generation of SEI film (solid electrolyte film), thus demonstrates relatively low efficiency first and poor cycle performance.
(2) the lithium ion battery Co that 0.5g step () is obtained2SnO4/ C negative material uniformly mixes with binding agent LA132 (agglomerant concentration is 0.033g/mL), conductive carbon Super-P of 0.067g of 3.01g, furnishing slurry, it is coated on Copper Foil, coating thickness is 100 microns, and is prepared as anode plate for lithium ionic cell 4 through dry 6 hours of 100 DEG C of vacuum, roll-in (thickness is 85 microns).
Measure of merit:
Anode plate for lithium ionic cell 1～4 obtained by embodiment 1～3 and comparative example 1 is assembled into simulated battery 1～4 respectively.Concrete operations and condition be: uses sheet-punching machine by the Co of above-mentioned preparation2SnO4/ C negative material fills into the circular piece of diameter of phi=18mm, it is pour lithium slice to electrode, electrolyte is that (solvent is ethylene carbonate (ethylene carbonate to 1mol/L LiPF6 solution, EC)+dimethyl carbonate (dimethy carbonate, DMC)+Ethyl methyl carbonate (Ethyl Methyl Carbonate, EMC) configuration of 1:1:1 in mass ratio forms), barrier film is microporous polypropylene membrane Celgard-2300, and in the glove box of full argon, assembling obtains CR2430 type button cell.
Simulated battery is carried out 1～4 and carries out performance test, use the charging and discharging capacity cycle performance of (Wuhan Jin Nuo Electronics Co., Ltd.) LAND battery test system test simulation battery 1～4 respectively, wherein, carrying out the experiment of constant current charge-discharge specific capacity loop test with the electric current of 1mA, charging/discharging voltage is limited in 0.01～3.00 volt.
Test result is as follows:
Fig. 7 is the charge-discharge performance figure of simulated battery 1, and the lithium ion battery cyclical stability of simulated battery 1 is relatively good as seen from the figure, and electric discharge and charge specific capacity are respectively 991.5mAh g first-1With 655.4mAh g-1, irreversible capacity is 31.5% first.After 50 charge and discharge cycles, material still keeps 564mAh g-1Specific discharge capacity, and coulombic efficiency is maintained at more than 95%, stable cycle performance.
Fig. 8 is the charge-discharge performance figure of simulated battery 2, and the lithium ion battery of simulated battery 2 specific capacity first is higher as seen from the figure, and electric discharge and charge specific capacity are respectively 1210.5mAh g first-1With 709.3mAh g-1, irreversible capacity is 41.4% first.After 50 charge and discharge cycles, material still keeps 630.2mAh g-1Specific discharge capacity, and coulombic efficiency is maintained at more than 95%, stable cycle performance.
Fig. 9 is the charge-discharge performance figure of simulated battery 3, and the lithium ion battery of simulated battery 3 specific capacity first is high as seen from the figure, and electric discharge and charge specific capacity are respectively 1378.5mAh g first-1With 802.6mAh g-1, irreversible capacity is 41.8% first.After 50 charge and discharge cycles, material keeps 618.7mAh g-1Specific discharge capacity, and coulombic efficiency is maintained at more than 95%, stable cycle performance.
Figure 10 is the charge-discharge performance figure of simulated battery 4, and the lithium ion battery first discharge specific capacity of simulated battery 4 is high, up to 1220.8mAh g as seen from the figure-1, but initial charge specific capacity is the lowest, only 645.7mAh g-1, efficiency is poor first.Circulation volume sharp-decay in 50 discharge and recharges, only keeps 200mAh g-1Specific discharge capacity, coulombic efficiency is low, and cycle performance is poor.
The charge-discharge performance of simulated battery 4 is that in the anode plate for lithium ionic cell 4 of simulated battery 4 contained ion cathode material lithium not carbon containing than the reason of simulated battery 1,2 and 3 difference, thus cannot alleviate bulk effect big in charge and discharge process and capacity attenuation；And the pure cobaltous stannate of ball milling will cause the pulverizing of cobaltous stannate crystalline particles and rupture, material is caused to form too much SEI film (solid electrolyte film) in charge and discharge process；In addition the electrical conductivity of material is poor, and these reasons are all unfavorable for the increase of capacity of lithium ion battery.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify; all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. a lithium ion battery Co2SnO4The preparation method of/C nano composite negative pole material, it is characterised in that
Comprise the following steps:
(1) pink salt and cobalt salt are dissolved in dispersant obtain dispersion liquid, then to dispersion under conditions of stirring
In liquid, the speed with 5～15mL/min drips sodium hydroxide solution, stirring reaction 10～20min after dripping,
Filter or centrifuging and taking precipitation, precipitation vacuum drying is obtained powder；
(2) after the powder that step (1) obtains being placed under inert gas environment and is warming up to 900～950 DEG C
Reaction 6～12h, obtains product, then by product and graphite mechanical ball milling 12～48h；
(3) the product nano ball milling 8～24h that step (2) mechanical ball milling is obtained, the solution that then will obtain
Centrifuging and taking precipitate, then by washing of precipitate, be dried, obtain described lithium ion battery Co2SnO4/ C nano is combined
Negative material；
In step (2), product is (3:7)～(7:3) with the mass ratio of graphite.
Preparation method the most according to claim 1, it is characterised in that the stannum described in step (1)
Salt is solubility pink salt, and described cobalt salt is soluble cobalt, and described dispersant is deionized water；Described point
Dissipating the mol ratio of tin ion and cobalt ion in liquid is 1:2.
Preparation method the most according to claim 2, it is characterised in that described solubility pink salt is chlorination
One in stannum, nitric acid stannum or STANNOUS SULPHATE CRYSTALLINE；Described soluble cobalt is in cobaltous chloride, cobalt nitrate or cobaltous sulfate
One.
Preparation method the most according to claim 1, it is characterised in that step drips hydrogen in (1)
In reactant liquor after sodium hydroxide solution, the concentration of sodium hydroxide is 2mol/L；Described vacuum drying temperature is
60～90 DEG C, the vacuum drying time is 8～12h；Described mixing speed is 100～500r/min.
Preparation method the most according to claim 1, it is characterised in that inertia described in step (2)
Gas is nitrogen or the argon of purity 99.999% of purity 99.999%；Described programming rate is 2～5 DEG C/min；
Described graphite is native graphite, electrographite or modified graphite.
Preparation method the most according to claim 1, it is characterised in that product in step (2)
It is the zirconia ball of 3～10mm with addition particle diameter before graphite ball milling；Product and the mixture of graphite and oxygen
The mass ratio changing zirconium ball is (70～75): 1, and mechanical ball milling speed is 300～350r/s.
Preparation method the most according to claim 1, it is characterised in that nanometer described in step (3)
Rotational speed of ball-mill is 3500～3800r/min；Described washing is that dehydrated alcohol and deionized water alternately rinse several times；
Described baking temperature is 60 DEG C, and drying time is 8h.
8. the lithium ion battery Co that preparation method described in any one of claim 1～7 obtains2SnO4/ C nano is multiple
Close negative material.
9. the lithium ion battery Co that preparation method described in any one of claim 1～7 obtains2SnO4/ C nano is multiple
Close negative material application in preparing anode plate for lithium ionic cell, it is characterised in that comprise the steps:
By lithium ion battery Co2SnO4/ C nano composite negative pole material, binding agent and conductive agent press (75～85):
(15～5): be coated on Copper Foil after the mass ratio mixing of 10, laggard in 50～100 DEG C of vacuum drying 5～24h
Row roll-in, obtains anode plate for lithium ionic cell.
Application the most according to claim 9, it is characterised in that described binding agent is binding agent LA132
Or polyvinylidene fluoride；Described conductive agent is conductive carbon black or nano-sized carbon；
Described lithium ion battery Co2SnO4The mass ratio of/C nano composite negative pole material, binding agent and conductive agent
For 75:15:10；
Described coating thickness is 100～180 microns；Roll-in thickness is 75～150 microns.
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| CN105514327A (en) * | 2015-12-09 | 2016-04-20 | 宋宏婷 | Lithium polymer battery |
| CN105449260A (en) * | 2015-12-09 | 2016-03-30 | 宋宏婷 | Polymer battery |
| CN107611373A (en) * | 2015-12-09 | 2018-01-19 | 宋宏婷 | A kind of nano Co2SnO4Polysulfonate acid naphthalene electrode and its application |
| CN106784751A (en) * | 2017-03-24 | 2017-05-31 | 南昌专腾科技有限公司 | A kind of preparation method and system of tin pewter composite negative pole material |
| CN107694580B (en) * | 2017-09-07 | 2019-12-27 | 电子科技大学 | Nano composite selenide and preparation method thereof |
| CN110034273B (en) * | 2018-01-12 | 2022-04-15 | 中南大学 | Sn-based sulfide and/or nitride modified tin oxide thin-film lithium battery cathode and preparation and application thereof |
| CN108817413B (en) * | 2018-05-04 | 2021-07-20 | 同济大学 | Preparation of CoSnO3Method for @ Au amorphous nano cube |
| CN109088057B (en) * | 2018-07-09 | 2021-07-13 | 河北师范大学 | Method for preparing lithium battery cathode additive by calcining organic tin compound |
| CN108807945A (en) * | 2018-07-27 | 2018-11-13 | 上海工程技术大学 | Redox graphene/stannate anode material of lithium-ion battery and its preparation method and application |
| CN111200126A (en) * | 2020-01-17 | 2020-05-26 | 三峡大学 | Preparation method of amorphous tin/carbon material as lithium ion battery negative electrode material |
| CN114195198B (en) * | 2021-11-30 | 2023-04-21 | 西安航空学院 | Co 2 SnO 4 Cc/S composite material and titanium dioxide induced growth method and application thereof |
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| CN102760885B (en) * | 2012-07-23 | 2014-08-13 | 浙江大学 | Tin-base complex oxide/graphene composite material, and preparation method and application thereof |
| CN103531758B (en) * | 2013-09-11 | 2016-04-06 | 安泰科技股份有限公司 | Nano metal tin and composite cathode material of silicon/carbon/graphite and preparation method thereof |
| CN103730660A (en) * | 2013-11-26 | 2014-04-16 | 沃太能源南通有限公司 | Preparation method of modified graphite anode material for lithium ion battery |
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| Synthesis of Co2SnO4@C core-shell nanostructures with reversible lithium storage;Yue Qi 等;《Journal of Power Sources》;20110826(第196期);第10234-10239页 * |
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