CN106898775A - Double cladded type richness lithium materials in a kind of surface and preparation method thereof - Google Patents
Double cladded type richness lithium materials in a kind of surface and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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Abstract
The present invention discloses double cladded type richness lithium materials in a kind of surface and preparation method thereof.The double cladded type richness lithium materials in the surface are the composite formed in the outer surface of rich lithium material successively particles cladded by metallic compound layer and carbon-coating；The chemical formula of rich lithium material is Li1+xMnyMzAwOr, M is at least one in Ni, Co, Al, Mg, Ti, Fe, Cu, Cr, Mo, Zr, Ru and Sn, and A is at least one in S, P, B and F, and 0 ＜ x≤1,0 ＜ y≤1,0≤z ＜ 1,0≤w≤0.2,1.8≤r≤3.Its preparation method is：Prepare soluble metal salt solution；Rich lithium material is immersed in the solution, precipitating reagent is added, stirring, filtering is dried, heat treatment；Sample after heat treatment is impregnated into the solution of carbonaceous sources and is stirred, dried；Dried sample is heated into carbonization under protective atmosphere, the rich lithium material of the double cladded types in surface is obtained.The present invention can improve the stability and electrical conductivity of material structure, improve the cycle performance and high rate performance of rich lithium material.
Description
Technical field
The present invention relates to double cladded type richness lithium materials in a kind of surface and preparation method thereof, belong to lithium ion battery skill
Art field.
Background technology
With fossil energy increasingly depleted and environmental problem it is increasingly serious, that finds other high-efficiency environment friendlies can
It is a kind of secondary cell with repeatable discharge and recharge feature to substitute lithium ion battery, is developed so far existing more than 20
The history in year, its application is related to the numerous areas such as communication, traffic, military affairs, medical treatment, amusement.In recent years
With the fast development of electric automobile etc., high specific energy, high power lithium ion cell turn into following lithium ion battery
The inevitable direction of development.Current commercialized positive electrode mainly has LiCoO2、LiFePO4、LiMn2O4、
Ternary material, its specific capacity is below 200mAh/g.Positive electrode is the principal element for limiting battery specific energy,
Therefore in order to develop high specific energy batteries, it is felt to be desirable to find the positive electrode with more height ratio capacity.
In recent years, rich lithium material because capacity is high, security is good, low cost and cause the extensive concern of people.
Its specific capacity is generally more than 250mAh/g, be even up in the report having 300mAh/g (Nano Lett.,
2008,8 (3)：957-961).Although rich lithium material capacity is high, its cycle performance and high rate performance all compare
Difference, so as to constrain its commercialized application.Therefore rich lithium material is modified, to greatly improve it
Cycle performance and high rate performance.
The main method for improving rich lithium material chemical property at present be coat or adulterate (Adv.Mater.2012,
24,1192-1196；Adv.Funct.Mater.2014,1-7).Because carbon material has high electronic conductance
Rate, LiFePO4 its capacity and high rate performance after carbon coated are all significantly improved, present carbon coating
Have become a common method for improving LiFePO 4 material.But use liquid phase coating for rich lithium material
Carbon, because carbon source can react with metal oxide in carbonisation, destroys the structure of material, makes
Chemical property becomes very poor, so using the carbon coating of liquid phase method richness lithium material difficult to realize.There is document report
Road is using thermal evaporation deposition (Electrochemistry Communications, 2010,12：750-753) and direct current
Magnetron sputtering (Electrochimica Acta, 2012,63：Method 112-117) is on the pole piece of rich lithium material
Carbon is deposited to realize carbon coating.These methods are very high due to being limited by equipment and carbon source, one side cost,
On the other hand it is difficult to carry out large batch of cladding, and the pole piece made with rich lithium material in advance can only be deposited on
On, it is impossible to realize comprehensive cladding of material granule.So the method for needing realizes the carbon of rich lithium material
Cladding.
The content of the invention
It is an object of the invention to overcome the shortcomings of existing method, there is provided a kind of double cladded type richness lithium materials in surface,
Avoid during carbonization treatment rich lithium material and the directly contact of carbon source and react, destroy its structure.
Preparation method another object of the present invention is to provide a kind of double cladded type richness lithium materials in surface,
The method covered by double-contracting improves the stability and electrical conductivity of material structure, improves the cyclicity of rich lithium material
Energy and high rate performance.
To achieve the above object, the present invention uses following technical scheme：
A kind of double cladded type richness lithium materials in surface, the double cladded type richness lithium materials in the surface are in the outer of rich lithium material
Surface particles cladded by metallic compound layer and carbon-coating and the composite that is formed successively；The chemical formula of the rich lithium material
It is Li1+xMnyMzAwOr, wherein M be Ni, Co, Al, Mg, Ti, Fe, Cu, Cr, Mo, Zr,
At least one in Ru and Sn, A is at least one in S, P, B and F, and 0 ＜ x≤1,0 ＜ y
≤ 1,0≤z ＜ 1,0≤w≤0.2,1.8≤r≤3.
Wherein, the metallic compound is in Sn, Ti, Al, Mg, Zr, Zn, Cr, V, Fe and Mo
The corresponding oxide of at least one metal, fluoride or phosphate.
The quality of the two-coat that the metal compound layer and carbon-coating are constituted accounts for whole composite
0.01-10%, the mass ratio in the two-coat between carbon and metallic compound is 1: 10-10: 1.
A kind of preparation method of the double cladded type richness lithium materials in surface, at least comprises the following steps：
(1) soluble metallic salt is weighed, dissolving is configured to soluble metal salt solution；By rich lithium material dipping
In metal salt solution, precipitating reagent is subsequently adding；
(2) above-mentioned solution is stirred, filtering is dried, heat treatment；Specially：By above-mentioned solution in 0-90
DEG C stirred in water bath 10min-12h, filtering, 1-12h is dried then at 50-150 DEG C, then in 200-700
DEG C heat treatment 10min-20h；
(3) sample after heat treatment is impregnated into the solution containing carbon source and is stirred, dried；Specially：Will
Sample after heat treatment is impregnated into the solution containing carbon source and is persistently stirred in 5-90 DEG C of water-bath
10min-12h, until liquid is evaporated, then dries 1-12 hours in 50-150 DEG C；
(4) dried sample is heated into carbonization under protective atmosphere, obtains the rich lithium material of the double cladded types in surface
Material.
Wherein, the soluble metallic salt is Sn, Ti, Al, Mg, Zr, Zn, Cr, V, Fe, Mo
Soluble-salt at least one.The concentration of soluble metal salt solution is 0.001-10mol/L.
The precipitating reagent is at least one in hydroxide, urea, fluoride, phosphate.Wherein, institute
It is at least one in lithium hydroxide, NaOH, potassium hydroxide and ammoniacal liquor to state hydroxide；The fluorination
Thing is at least one in ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride；The phosphate be ammonium phosphate,
At least one in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate, potassium phosphate.
The carbon source is sucrose, glucose, maltose, citric acid, polypropylene, polyvinyl alcohol, carboxymethyl
At least one in cellulose, polyacrylamide, starch, phenolic resin and pitch.
Drying means used is heat drying, forced air drying, vacuum in step (2) and step (3)
Dry, spray drying, any one in microwave drying and centrifugal drying.
In step (2), heat treatment temperature is 200-700 DEG C, and soaking time is 10min-20h.
In step (4), the protective atmosphere is in nitrogen, argon gas, hydrogen and its arbitrary proportion gaseous mixture
One kind.The carburizing temperature is 200-800 DEG C, and soaking time is 10min-20h.
The advantage of the invention is that：
Then the present invention coats one layer of carbon again by first coating layer of metal compound in the outside of rich lithium material,
So as to form surface two-coat.This mode causes that carbon source does not connect directly in carbonisation with rich lithium material
Touch, redox reaction occurs with carbon source so as to avoid the rich lithium material during carbonization treatment, cause material
Material structural damage and the decay of performance.
Of the invention pair of clad structure greatly improves the surface electronic conductance and ionic conductance of rich lithium material, makes
The charging and discharging capacity of material, efficiency and cycle performance are all significantly improved.
Preparation process of the present invention is simple, with low cost, as a result favorable reproducibility.
Brief description of the drawings
Fig. 1 is Li [Li prepared in comparative example 1, comparative example 2 and embodiment 10.20Ni0.13Co0.13Mn0.54]O2
Material, TiO2Cladding Li [Li0.20Ni0.13Co0.13Mn0.54]O2TiO is covered in material and surface double-contracting2With C's
Li[Li0.20Ni0.13Co0.13Mn0.54]O2The XRD of material.
Fig. 2 is Li [Li prepared in comparative example 10.20Ni0.13Co0.13Mn0.54]O2Material (Fig. 2 a), reality
Apply prepared surface double-contracting in example 1 and cover TiO2With the Li [Li of C0.20Ni0.13Co0.13Mn0.54]O2Material (figure
SEM spectrum 2b).
Fig. 3 is Li [Li prepared in comparative example 1, comparative example 2 and embodiment 10.20Ni0.13Co0.13Mn0.54]O2
Material, TiO2Cladding Li [Li0.20Ni0.13Co0.13Mn0.54]O2TiO is covered in material and surface double-contracting2With C's
Li[Li0.20Ni0.13Co0.13Mn0.54]O2The discharge capacity comparison diagram under different current densities of material.
Fig. 4 is Li [Li prepared in comparative example 1, comparative example 2 and embodiment 10.20Ni0.13Co0.13Mn0.54]O2
Material, TiO2Cladding Li [Li0.20Ni0.13Co0.13Mn0.54]O2TiO is covered in material and surface double-contracting2With C's
Li[Li0.20Ni0.13Co0.13Mn0.54]O2The cycle performance comparison diagram of material.
Specific embodiment
The present invention is described in further detail below in conjunction with drawings and Examples, but the implementation method invented is not
It is only limitted to this.
Comparative example 1
Rich lithium material Li [Li0.20Ni0.13Co0.13Mn0.54]O2Illustrative preparation method：
Step 1, precursor synthesis
Ratio (Li: Ni: Co: Mn=1.20: 0.13: 0.13: 0.54) according to the amount of material weighs nickel protoxide, oxygen
Change cobalt, manganese dioxide and lithium carbonate, after mixing 12h in batch mixer, add in the ratio of solid content 20wt%
Enter deionized water, then pour into ball mill with the rotating speed ball milling 5h of 1000r/min slurry.Finally incite somebody to action
The slurry spray drying arrived, that is, obtain Li [Li0.20Ni0.13Co0.13Mn0.54]O2Presoma.
Step 2, high temperature sintering
Presoma is warmed up to 500 DEG C with the heating rate of 5 DEG C/min, 6h is incubated, then proceedes to be warmed up to
800 DEG C, it is incubated 12h；Room temperature is finally naturally cooling to, that is, obtains Li [Li0.20Ni0.13Co0.13Mn0.54]O2Material
Material.
Obviously, the preparation Li [Li described in the present embodiment0.20Ni0.13Co0.13Mn0.54]O2Method is not regarded as right
Li1+xMnyMzAwOrThe restriction of material preparation method, those skilled in the art are also an option that other well known
Method prepares Li1+xMnyMzAwOrMaterial.
Comparative example 2
Rich lithium material Li [Li0.20Ni0.13Co0.13Mn0.54]O2Surface coating TiO2Illustrative preparation method, its
Step is as follows：
By 10g richness lithium material Li [Li0.20Ni0.13Co0.13Mn0.54]O230mL is immersed in dissolved with 0.51g metatitanic acids four
In the ethanol solution of butyl ester, after persistently stirring 6h in 25 DEG C of water-bath, three times, 120 are washed in filtering
DEG C drying 12 hours, sinters 4 hours then at 400 DEG C, that is, obtain 1wt%TiO2Cladding
Li[Li0.20Ni0.13Co0.13Mn0.54]O2Composite.
Equally, the preparation TiO described in the present embodiment2Cladding Li [Li0.20Ni0.13Co0.13Mn0.54]O2Method simultaneously
It is not intended as coating Li to metallic compound1+xMnyMzAwOrComposite material and preparation method thereof restriction, this area
Technical staff is also an option that other well known method prepares metallic compound cladding Li1+xMnyMzAwOrAnswer
Condensation material.
Embodiment 1
The preparation side of the rich lithium material that the double-contracting of a kind of surface clad oxide of the present embodiment offer and carbon is covered
Method, it comprises the following steps：
(1) metal oxide clad (TiO2) preparation：
By 10g richness lithium material Li [Li0.20Ni0.13Co0.13Mn0.54]O2Being immersed in 30mL and being added dropwise has 0.51g metatitanic acids
In the ethanol solution of four butyl esters, after persistently stirring 6 hours in 15 DEG C of water-bath, filtering is washed three times,
Dried 4 hours in 100 DEG C of vacuum constant-temperature container, sintered 2 hours then at 500 DEG C, that is, obtain TiO2Covering amount
It is the Li [Li of 1wt%0.20Ni0.13Co0.13Mn0.54]O2Composite.
(2) preparation of carbon coating layer：
TiO has been coated by above-mentioned2Li [Li0.20Ni0.13Co0.13Mn0.54]O2Material, be impregnated into 15mL dissolved with
In the aqueous solution of 0.33g sucrose, persistently stirred in 80 DEG C of water-bath, until liquid is evaporated, then in 100
DEG C vacuum constant-temperature container in dry 5 hours；
By above-mentioned dried sample, after being warmed up to 400 DEG C with the heating rate of 3 DEG C/min under an argon atmosphere
Insulation 0.5 hour, that is, obtain surface double-contracting and cover TiO2With the rich lithium material of carbon, TiO2Material is accounted for carbon total
The 1wt% of quality.
Target product X RD is schemed as shown in figure 1, compare with comparative example 1 and comparative example 2 from figure, can be with
XRD is not changed in substantially before and after finding out cladding, illustrates that cladding does not have to the basic layer structure of rich lithium material
Influence；Its scanning electron microscope (SEM) photograph is as shown in Fig. 2 it can be seen that after two-coat is coated compared with comparative example 1
One layer of carbon is equably coated in the outside of particle.
With material obtained above as positive electrode, with lithium piece as negative material, button cell is assembled into,
Constant current charge-discharge test is carried out under the conditions of 25 DEG C, voltage range is：2~4.8V.As shown in figure 3, being cladding
Discharge capacity contrast of the front and rear rich lithium material under different current densities.From the figure, it can be seen that
Under the current density of 20mA/g, the discharge capacity of richness lithium material is approached before and after cladding, about 280mAh/g, but
It is, with the increase of current density, to coat TiO2The discharge capacity of material somewhat declines；TiO is covered in double-contracting2With carbon
Rich lithium material discharge capacity is higher than uncoated material, such as under the current density of 200mA/g, comparative example 1,
The discharge capacity of comparative example 2 and embodiment 1 is respectively 215.8mAh/g, 211.3mAh/g and 225mAh/g,
Under the current density of 600mA/g, discharge capacity is respectively 157mAh/g, 151mAh/g and 179mAh/g.
It can be seen that TiO is covered in double-contracting2High rate performance with rich lithium material after carbon is significantly improved.Fig. 4 is richness lithium before and after cladding
The cycle performance contrast of material, test current density is 200mA/g, and potential region is 2.5-4.6V.From figure
It can be seen that uncoated material, cladding TiO2TiO is covered in material and double-contracting2With the initial discharge of the rich lithium material of carbon
Capacity is respectively 189mAh/g, 186mAh/g and 192mAh/g, the discharge capacity point after circulating 200 weeks
The capability retention for not dropping to 134.7mAh/g, 148.4mAh/g and 159.3mAh/g, i.e., 200 week is respectively
71%th, 79.8% and 82.9%.After visible surface double-contracting is covered, the high rate performance and cycle performance of rich lithium material are all
It is greatly improved.
The electrochemical property test data of prepared material are shown in Table 1 in the present embodiment and comparative example.
Embodiment 2
The present embodiment provides the preparation method of the rich lithium material of a kind of double coated metal oxides in surface and carbon, its
Comprise the following steps：
(1) metal oxide clad (ZrO2) preparation：
By 10g richness lithium material Li [Li0.20Ni0.13Co0.13Mn0.54]O225mL is immersed in dissolved with 0.16g isopropanols
In the aqueous isopropanol of zirconium, stirred 6 hours under 25 DEG C of air-proof conditions, be then stirred continuously until at 60 DEG C
Solution is evaporated, and is dried 6 hours in 100 DEG C of vacuum constant-temperature container, then is heated up with the heating rate of 5 DEG C/min
2 hours are incubated to 500 DEG C, that is, obtain ZrO2Li [the Li of cladding0.20Ni0.13Co0.13Mn0.54]O2Material, bag
The amount of covering is 0.5wt%.
(2) preparation of carbon coating layer：
ZrO has been coated by above-mentioned2Li [Li0.20Ni0.13Co0.13Mn0.54]O2Material, be impregnated into 20mL dissolved with
In the aqueous solution of 0.165g glucose, persistently stirred in 60 DEG C of water-bath, until liquid is evaporated, Ran Houyu
Dried 3 hours in 110 DEG C of vacuum constant-temperature container；
By above-mentioned dried sample, after being warmed up to 450 DEG C with the heating rate of 3 DEG C/min in a nitrogen atmosphere
Insulation 20 minutes, that is, obtain surface double-contracting and cover ZrO2With the rich lithium material of carbon, ZrO2Covering amount with carbon is equal
Account for the 0.5wt% of material gross mass.
ZrO is covered with surface double-contracting obtained above2With the Li [Li of carbon0.20Ni0.13Co0.13Mn0.54]O2Material is for just
Pole material is assembled into button cell, and pole piece preparation method, battery assembly method and method of testing are with embodiment 1.
The electrochemical property test data of material manufactured in the present embodiment are shown in Table 1.
Embodiment 3
The present embodiment provides the preparation method that the rich lithium material of metal fluoride and carbon is covered in a kind of surface double-contracting, its
Comprise the following steps：
(1) metal fluoride clad (AlF3) preparation：
By 10g richness lithium material Li [Li0.23Ni0.10Co0.10Mn0.57]O215mL is immersed in dissolved with 0.28g aluminum nitrates
The aqueous solution in, the aqueous solution of the 10mL dissolved with 0.4g ammonium fluorides is slowly added dropwise under conditions of stirring, be added dropwise
After mixed solution is persistently stirred into 3 hours in 50 DEG C of water-bath after complete, filtering is washed three times, 100 DEG C
Dried 4 hours in vacuum constant-temperature container, sintered 2 hours then at 400 DEG C, that is, obtain 1wt%AlF3Cladding
Li[Li0.23Ni0.10Co0.10Mn0.57]O2Composite.
(2) preparation of carbon coating layer：
AlF has been coated by above-mentioned3Li [Li0.23Ni0.10Co0.10Mn0.57]O2Material, be impregnated into 20mL dissolved with
In the aqueous solution of 0.33g glucose, persistently stirred in 60 DEG C of water-bath, until liquid is evaporated, Ran Houyu
Dried 5 hours in 100 DEG C of convection oven；
By above-mentioned dried sample, after being warmed up to 400 DEG C with the heating rate of 3 DEG C/min under an argon atmosphere
Insulation 0.5 hour, that is, obtain surface double-contracting and cover AlF3With the Li [Li of carbon0.23Ni0.10Co0.10Mn0.57]O2Material,
AlF3Covering amount with carbon accounts for the 1wt% of material gross mass.
AlF is covered with surface double-contracting obtained above3With the Li [Li of carbon0.23Ni0.10Co0.10Mn0.57]O2Composite
It is positive electrode, is assembled into button cell, pole piece preparation method, battery assembly method and method of testing is with real
Apply example 1.
The electrochemical property test data of material manufactured in the present embodiment are shown in Table 1.It is recognised that this reality from table
High rate performance, the cycle performance for applying material prepared by example are good.
Embodiment 4
The present embodiment provides the preparation method that the rich lithium material of metal phosphate and carbon is covered in a kind of surface double-contracting, its
Comprise the following steps：
(1) metal phosphate clad (AlPO4) preparation：
By 10g richness lithium material Li [Li0.13Ni0.27Mn0.54Co0.06]O2It is immersed in 15mL solution 0.21g aluminum nitrates
The aqueous solution in, solution of the 10mL dissolved with 0.27g sodium phosphates is slowly added dropwise under conditions of stirring, will be above-mentioned
After mixed solution persistently stirs 2 hours in 60 DEG C of water-bath, filtering, repeatedly washing, 100 DEG C of vacuum is permanent
Dried 3 hours in incubator, sintered 2 hours then at 500 DEG C, that is, obtain AlPO4Cladding
Li1.13[Ni0.27Mn0.54Co0.06]O2Material.
(2) preparation of carbon coating layer：
AlPO has been coated by above-mentioned4Li1.13[Ni0.27Mn0.54Co0.06]O2Material, be impregnated into 15mL dissolved with
In the aqueous solution of 0.165g sucrose, persistently stirred in 80 DEG C of water-bath, until liquid is evaporated, then in 110
DEG C vacuum constant-temperature container in dry 3 hours；
By above-mentioned dried sample, after being warmed up to 450 DEG C with the heating rate of 3 DEG C/min in a nitrogen atmosphere
Insulation 0.5 hour, that is, obtain Surface coating AlPO4With the Li of carbon1.13[Ni0.27Mn0.54C00.06]O2Material,
AlPO4With the 1wt% and 0.5wt% that the covering amount of carbon accounts for material gross mass respectively.
AlPO is covered with surface double-contracting obtained above4With the Li of carbon1.13[Ni0.27Mn0.54Co0.06]O2Material is for just
Pole material, is assembled into button cell, and pole piece preparation method, battery assembly method and method of testing are with embodiment 1.
The electrochemical property test data of material manufactured in the present embodiment are shown in Table 1.
Embodiment 5
The present embodiment provides the preparation method of the rich lithium material of a kind of double coated metal oxides in surface and carbon, its
Comprise the following steps：
(1) metal oxide clad (SnO2) preparation：
By 10g richness lithium materials Li1.13[Ni0.27Mn0.49Cr0.05Co0.06]O220mL is immersed in dissolved with 0.26g chlorine
Change tin the aqueous solution in, 10mL ammonia spirits are slowly added dropwise under conditions of stirring, by above-mentioned mixed solution in
After persistently stirring 5 hours at room temperature, after filtering, fully washing, dried 5 hours in 100 DEG C of convection ovens,
Sintered 2 hours then at 400 DEG C, that is, obtain SnO2The Li of cladding1.13[Ni0.27Mn0.49Cr0.05Co0.06]O2Material.
(2) preparation of carbon coating layer：
SnO has been coated by above-mentioned2Li1.13[Ni0.27Mn0.49Cr0.05Co0.06]O2Material, is impregnated into 20mL
In dissolved with the ethanol solution of 0.12g phenolic resin, persistently stirred in 40 DEG C of water-bath, until liquid is evaporated,
Then dried 6 hours in 110 DEG C of bellows；
By above-mentioned dried sample, 500 DEG C are warmed up to the heating rate of 5 DEG C/min under nitrogen and hydrogen mixture
2 hours are incubated afterwards, that is, obtain Surface coating SnO2With the Li of carbon1.13[Ni0.27Mn0.49Cr0.05Co0.06]O2Material
Material, SnO2Covering amount with carbon accounts for the 0.5wt% of material gross mass.
SnO is covered with surface double-contracting obtained above2With the Li of carbon1.13[Ni0.27Mn0.49Cr0.05Co0.06]O2Material
It is positive electrode, is assembled into button cell, pole piece preparation method, battery assembly method and method of testing is with real
Apply example 1.
The electrochemical property test data of material manufactured in the present embodiment are shown in Table 1.
Embodiment 6
The present embodiment provides the preparation method that the rich lithium material of metal phosphate and carbon is covered in a kind of surface double-contracting, its
Comprise the following steps：
(1) metal phosphate clad (FePO4) preparation：
By 10g richness lithium materials Li1.2[Ni0.20Mn0.60]O218mL is immersed in dissolved with the water-soluble of 0.186g iron chloride
In liquid, solution of the 20mL dissolved with 0.13g sodium phosphates is slowly added dropwise under conditions of stirring, above-mentioned mixing is molten
After liquid is persistently stirred 2 hours at room temperature, after filtering, fully washing, 5 are dried in 110 DEG C of convection ovens
Hour, sintered 2 hours then at 300 DEG C, that is, obtain FePO4The Li of cladding1.2[Ni0.20Mn0.60]O2Material.
(2) preparation of carbon coating layer：
FePO has been coated by above-mentioned4Li1.2[Ni0.20Mn0.60]O2Material, is impregnated into 35mL dissolved with 0.21g
In the ethanol solution of phenolic resin, persistently stirred in 40 DEG C of water-bath, until liquid is evaporated, then in 110
DEG C bellows in dry 6 hours；
By above-mentioned dried sample, 400 DEG C are warmed up to the heating rate of 5 DEG C/min under argon hydrogen gaseous mixture
1 hour is incubated afterwards, that is, obtains Surface coating FePO4With the Li of carbon1.2[Ni0.20Mn0.60]O2Material, FePO4
Covering amount with carbon accounts for the 1wt% of material gross mass.
FePO is covered with surface double-contracting obtained above4With the Li of carbon1.2[Ni0.20Mn0.60]O2Material is positive pole material
Material, is assembled into button cell, and pole piece preparation method, battery assembly method and method of testing are with embodiment 1.
The electrochemical property test data of material manufactured in the present embodiment are shown in Table 1.
Embodiment 7
The present embodiment provides the preparation method of the rich lithium material of a kind of double coated metal oxides in surface and carbon, its
Comprise the following steps：
(1) metal oxide clad (Al2O3) preparation：
By 10g richness lithium materials Li1.26[Ni0.10Mn0.59Mo0.03Co0.02]O215mL is immersed in dissolved with 1g nitric acid
In the aqueous solution of aluminium, the solution of ammoniacal liquor is slowly added dropwise under conditions of stirring, by above-mentioned mixed solution in room temperature
After persistently stirring 6 hours down, after filtering, fully washing, dried 3 hours in 100 DEG C of convection ovens, then
Sintered 4 hours in 400 DEG C, that is, obtain Al2O3The Li of cladding1.26[Ni0.10Mn0.59Mo0.03Co0.02]O2Material.
(2) preparation of carbon coating layer：
Al has been coated by above-mentioned2O3Li1.26[Ni0.10Mn0.59Mo0.03Co0.02]O2Material, is impregnated into 25mL
In dissolved with the ethanol solution of 0.33g sucrose, persistently stirred in 40 DEG C of water-bath, until liquid is evaporated, so
After dry 5 hours in 110 DEG C of bellows；
By above-mentioned dried sample, protected after being warmed up to 500 DEG C with the heating rate of 10 DEG C/min under a nitrogen
Temperature 0.5 hour, that is, obtain Surface coating Al2O3With the Li of carbon1.26[Ni0.10Mn0.59Mo0.03Co0.02]O2Material,
Al2O3With the 2wt% and 1wt% that the covering amount of carbon accounts for material gross mass respectively.
Al is covered with surface double-contracting obtained above2O3With the Li of carbon1.26[Ni0.10Mn0.59Mo0.03Co0.02]O2Material
It is positive electrode, is assembled into button cell, pole piece preparation method, battery assembly method and method of testing is with real
Apply example 1.
The electrochemical property test data of material manufactured in the present embodiment are shown in Table 1.
Embodiment 8
The present embodiment provides the preparation method of the rich lithium material of a kind of double coated metal oxides in surface and carbon, its
Comprise the following steps：
(1) preparation of metal oxide clad (MgO)：
By 10g richness lithium materials Li1.13[Ni0.30Mn0.48Fe0.08]O220mL is immersed in dissolved with 0.358g magnesium sulfate
The aqueous solution in, the aqueous solution of the 10mL dissolved with 0.4g NaOH is slowly added dropwise under conditions of stirring, will
After above-mentioned mixed solution is persistently stirred 6 hours at room temperature, after filtering, fully washing, dried in 100 DEG C of air blast
Dried 3 hours in case, sintered 4 hours then at 450 DEG C, that is, obtain MgO claddings
Li1.13[Ni0.30Mn0.48Fe0.08]O2Material.
(2) preparation of carbon coating layer：
By the above-mentioned Li for having coated MgO1.13[Ni0.30Mn0.48Fe0.08]O2Material, be impregnated into 10mL dissolved with
In the aqueous solution of 0.165g sucrose, persistently stirred in 80 DEG C of water-bath, until liquid is evaporated, then in 110
DEG C bellows in dry 5 hours；
By above-mentioned dried sample, it is incubated after being warmed up to 400 DEG C with the heating rate of 5 DEG C/min under argon gas
0.5 hour, that is, obtain the Li of Surface coating MgO and carbon1.13[Ni0.30Mn0.48Fe0.08]O2Material, MgO and
The covering amount of carbon accounts for the 1wt% and 0.5wt% of material gross mass respectively.
The Li of MgO and carbon is covered with surface double-contracting obtained above1.13[Ni0.30Mn0.48Fe0.08]O2Material is positive pole
Material, is assembled into button cell, and pole piece preparation method, battery assembly method and method of testing are with embodiment 1.
The electrochemical property test data of material manufactured in the present embodiment are shown in Table 1.
Embodiment 9
The present embodiment provides the preparation method of the rich lithium material of a kind of double coated metal oxides in surface and carbon, its
Comprise the following steps：
(1) preparation of metal oxide clad (ZnO)：
By 10g richness lithium materials Li1.2[Ni0.20Mn0.53Ti0.07]O215mL is immersed in dissolved with 0.424g zinc sulfate
In the aqueous solution, the aqueous solution of the 20mL dissolved with 0.3g urea is slowly added dropwise under conditions of stirring, will be above-mentioned mixed
After conjunction solution is persistently stirred 6 hours at room temperature, filtering after cyclic washing, is done in 100 DEG C of convection ovens
Dry 3 hours, sintered 4 hours then at 300 DEG C, that is, obtain the Li of ZnO claddings1.2[Ni0.20Mn0.53Ti0.07]O2
Material.
(2) preparation of carbon coating layer：
By the above-mentioned Li for having coated ZnO1.2[Ni0.20Mn0.53Ti0.07]O2Material, is impregnated into 30mL dissolved with 0.32g
In the ethanol solution of phenolic resin, persistently stirred in 60 DEG C of water-bath, until liquid is evaporated, then in 110
DEG C bellows in dry 8 hours；
By above-mentioned dried sample, it is incubated after being warmed up to 400 DEG C with the heating rate of 5 DEG C/min under argon gas
0.5 hour, that is, obtain the Li of Surface coating ZnO and carbon1.2[Ni0.20Mn0.53Ti0.07]O2Material, ZnO and carbon
Covering amount account for 1 and 1.5wt% of material gross mass respectively.
The Li of ZnO and carbon is covered with surface double-contracting obtained above1.2[Ni0.20Mn0.53Ti0.07]O2Material is positive pole
Material, is assembled into button cell, and pole piece preparation method, battery assembly method and method of testing are with embodiment 1.
The electrochemical property test data of material manufactured in the present embodiment are shown in Table 1.
Embodiment 10
The present embodiment provides the preparation method that the rich lithium material of metal fluoride and carbon is covered in a kind of surface double-contracting, its
Comprise the following steps：
(1) metal fluoride clad (MgF2) preparation：
By 10g richness lithium materials Li1.17[Ni0.26Mn0.48Co0.10]O215mL is immersed in dissolved with 0.358g magnesium sulfate
The aqueous solution in, the aqueous solution of the 15mL dissolved with 0.42g sodium fluorides is slowly added dropwise under conditions of stirring, will be upper
State mixed solution at room temperature persistently stir 6 hours after, filtering, after washing, in 105 DEG C of vacuum drying ovens do
Dry 5 hours, sintered 4 hours then at 400 DEG C, that is, obtain MgF2The Li of cladding1.17[Ni0.26Mn0.48Co0.10]O2
Material.
(2) preparation of carbon coating layer：
MgF has been coated by above-mentioned2Li1.17[Ni0.26Mn0.48Co0.10]O2Material, be impregnated into 15mL dissolved with
In the aqueous solution of 0.38g sucrose, persistently stirred in 60 DEG C of water-bath, until liquid is evaporated, then in 110
DEG C bellows in dry 6 hours；
By above-mentioned dried sample, it is incubated after being warmed up to 500 DEG C with the heating rate of 5 DEG C/min under argon gas
1 hour, that is, obtain Surface coating MgF2With the Li of carbon1.17[Ni0.26Mn0.48Co0.10]O2Material, MgF2With
The covering amount of carbon accounts for the 1wt% of material gross mass respectively.
MgF is covered with surface double-contracting obtained above2With the Li of carbon1.17[Ni0.26Mn0.48Co0.10]O2Material is for just
Pole material, is assembled into button cell, and pole piece preparation method, battery assembly method and method of testing are with embodiment 1.
The electrochemical property test data of material manufactured in the present embodiment are shown in Table 1.
The electrochemical property test tables of data of prepared material in the embodiment of the present invention of table 1 and comparative example
Claims (13)
1. double cladded types richness lithium materials in a kind of surface, it is characterised in that the double cladded types richness lithium materials in the surface are
In the composite that the outer surface of rich lithium material successively particles cladded by metallic compound layer and carbon-coating are formed；The richness
The chemical formula of lithium material is Li1+xMnyMzAwOr, wherein M be Ni, Co, A1, Mg, Ti, Fe, Cu,
At least one in Cr, Mo, Zr, Ru and Sn, A is at least one in S, P, B and F, and 0
＜ x≤1,0 ＜ y≤1,0≤z ＜ 1,0≤w≤0.2,1.8≤r≤3.
2. double cladded types richness lithium materials in surface as claimed in claim 1, it is characterised in that the metallization
Compound is that at least one metal in Sn, Ti, A1, Mg, Zr, Zn, Cr, V, Fe and Mo is corresponding
Oxide, fluoride or phosphate.
3. double cladded types richness lithium materials in surface as claimed in claim 1, it is characterised in that the metallization
The quality of the two-coat that compound layer and carbon-coating are constituted accounts for the 0.01-10% of whole composite, the two-coat
Mass ratio between middle carbon and metallic compound is 1: 10-10: 1.
4. a kind of preparation method of the double cladded type richness lithium materials in surface any one of claim 1-3,
Characterized in that, at least comprising the following steps：
(1) soluble metallic salt is weighed, dissolving is configured to soluble metal salt solution；By rich lithium material dipping
In metal salt solution, precipitating reagent is subsequently adding；
(2) above-mentioned solution is stirred, filtering is dried, heat treatment；
(3) sample after heat treatment is impregnated into the solution containing carbon source and is stirred, dried；
(4) dried sample is heated into carbonization under protective atmosphere, obtains the rich lithium material of the double cladded types in surface
Material.
5. preparation method as claimed in claim 4, it is characterised in that the soluble metallic salt be Sn,
At least one in the soluble-salt of Ti, A1, Mg, Zr, Zn, Cr, V, Fe, Mo.
6. preparation method as claimed in claim 4, it is characterised in that the soluble metal salt solution
Concentration is 0.001-10mol/L.
7. preparation method as claimed in claim 4, it is characterised in that the precipitating reagent be hydroxide,
At least one in urea, fluoride, phosphate.
8. preparation method as claimed in claim 7, it is characterised in that the hydroxide be lithium hydroxide,
At least one in NaOH, potassium hydroxide and ammoniacal liquor；The fluoride is ammonium fluoride, sodium fluoride, fluorine
Change at least one in potassium, lithium fluoride；The phosphate be ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate,
At least one in sodium phosphate, potassium phosphate.
9. preparation method as claimed in claim 4, it is characterised in that the carbon source be sucrose, glucose,
Maltose, citric acid, polypropylene, polyvinyl alcohol, carboxymethylcellulose calcium, polyacrylamide, starch, phenol
At least one in urea formaldehyde and pitch.
10. preparation method as claimed in claim 4, it is characterised in that the drying means is dry for heating
Any one in dry, forced air drying, vacuum drying, spray drying, microwave drying and centrifugal drying.
11. preparation methods as claimed in claim 4, it is characterised in that the heat treatment temperature is 200-700
DEG C, soaking time is 10min-20h.
12. preparation methods as claimed in claim 4, it is characterised in that the protective atmosphere be nitrogen,
One kind in argon gas, hydrogen and its arbitrary proportion gaseous mixture.
13. preparation methods as claimed in claim 4, it is characterised in that the carburizing temperature is 200-800
DEG C, soaking time is 10min-20h.
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| CN108172803A (en) * | 2017-12-30 | 2018-06-15 | 国联汽车动力电池研究院有限责任公司 | Cladded type richness lithium material that a kind of surface is modified and preparation method thereof and lithium ion battery |
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| CN109244447A (en) * | 2018-09-26 | 2019-01-18 | 合肥国轩高科动力能源有限公司 | A kind of cladded type nickle cobalt lithium manganate tertiary cathode material and its preparation method and application |
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| CN110416525A (en) * | 2019-08-08 | 2019-11-05 | 上海华谊（集团）公司 | The composite material and preparation method of phosphoric acid manganese iron lithium with core-shell structure |
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| CN111302406B (en) * | 2020-02-25 | 2021-04-09 | 西安交通大学 | High-performance sphere-like porous ternary positive electrode precursor material and solid-phase preparation method thereof |
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| CN113675404A (en) * | 2021-08-13 | 2021-11-19 | 惠州亿纬锂能股份有限公司 | Lithium-rich manganese-based positive electrode material and preparation method and application thereof |
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