CN107681138A - A kind of lithium base high temperature inhales carbon material modified anode material, preparation method and the usage - Google Patents
A kind of lithium base high temperature inhales carbon material modified anode material, preparation method and the usage Download PDFInfo
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Abstract
The invention discloses a kind of lithium base high temperature to inhale carbon material modified anode material, its preparation method and the purposes in lithium ion battery.The lithium base high temperature of the present invention is inhaled carbon material modified anode material and is made up of positive electrode and lithium base high temperature suction carbon material, is specially：Lithium base high temperature inhales carbon material clad anode material and forms primary particle, bridge joint the primary particle composition second particle, and coats the second particle and form modified anode material.The modified anode material of the present invention is in multilayer coating structure shape, covered effect caused by this structure is excellent and electric conductivity is remarkably reinforced, when applied to battery, a part of lithium deintercalation that lithium base high temperature is inhaled in carbon material enters negative pole, the lithium of consumption required for compensate for the generation of negative pole SEI films, improve the utilization rate of lithium；Multiple cladding effectively reduces the Volume Changes in charge and discharge process, reduces the formation of positive electrode micro-crack, while effectively with electrolyte side reaction occurs for barrier positive electrode, improves the security performance and cycle performance of material.
Description
Technical field
The invention belongs to field of lithium ion battery anode, is related to a kind of modified anode material, its preparation method and use
On the way, more particularly to a kind of lithium base high temperature inhales carbon material modified anode material, its preparation method and the purposes in lithium ion battery.
Background technology
With increasingly wider, the energy density, safety to anode material for lithium-ion batteries of lithium ion battery applications scope
Higher and higher requirement is proposed with service life.
Anode active material of lithium ion battery is the critical material of lithium ion battery, energy density to lithium ion battery,
Safety and service life have a great influence, common anode active material of lithium ion battery have LiFePO4, cobalt acid lithium, LiMn2O4,
Nickle cobalt lithium manganate, nickel cobalt lithium aluminate and rich lithium material etc., wherein, the nickelic positive electrode of lithium ion battery has higher-energy close
Degree, it is considered to be most have one of positive electrode of application prospect.
The security performance and service life of the lithium ion battery of positive electrode are used as using lithium ion battery high-nickel material at present
It is to be improved.Numerous studies show, due to the moisture and two in the nickelic positive electrode surface residual lithium of lithium ion battery and air
Carbonoxide, which reacts, generates lithium hydroxide and lithium carbonate, remaining when the nickelic positive electrode of lithium ion battery is with electrolyte contacts
With electrolyte side reaction can occur for lithium and moisture, so as to cause the deterioration of battery, reduce the security performance and service life of battery.
Therefore, the residual alkali and moisture problem of nickelic positive electrode how are improved, to the lithium-ion electric using high-nickel material as positive electrode
The safety and service life in pond have very important significance.
Currently for the lithium ion battery storage using high-nickel material as positive electrode and security performance and cycle performance
Problem, solution method are concentrated mainly on the cladding of surface metal oxide, the cladding of surface polymer and surface treatment etc. and changed
Property means.As CN 104362330A disclose a kind of Surface coating boron lithium composite xoide nickel-cobalt lithium manganate cathode material and
Its preparation method, by the mixing alcoholic solution of lithium source and boron source, adding the nickle cobalt lithium manganate prepared, ultrasound makes for the invention
Its is dispersed in the solution, adds dispersant, sufficiently makes material infiltration in the solution, is thermally treated resulting in after evaporation solvent
Surface coating α-Li4B2O5Nickel-cobalt lithium manganate cathode material, the invention passes through in positive electrode Surface coating boron lithium combined oxidation
Thing, the diffusion coefficient of lithium ion is improved, enhance the ionic conductivity of material, while effectively avoid electrolyte and positive electrode
Direct contact, reduce electrode side reaction generation, so as to improve the chemical stability of positive electrode and cycle performance.But the party
Method complex procedures by material, it is necessary to be stirred scattered and post processing, while surface residual lithium does not remove, can not solve
The side reaction of remaining lithium and electrolyte occurs.
Therefore, it is necessary to research and develop, a kind of cladding process is simple, the more preferable and can simultaneously of covered effect removes material surface remnants
The method of lithium, to improve the generation of the nickelic positive electrode of lithium ion battery and electrolyte side reaction, larger lift lithium-ion electric
The nickelic positive electrode security in pond and cycle performance, technology branch is provided for the nickelic positive electrode broader applications of lithium ion battery
Hold.
The content of the invention
In view of the shortcomings of the prior art, inhale carbon material it is an object of the invention to provide a kind of lithium base high temperature and be modified positive pole material
Material, its preparation method and the purposes in lithium ion battery.The modified anode material of the present invention is in multilayer coating structure shape, this structure production
Raw covered effect is excellent and electric conductivity is remarkably reinforced, and when applied to battery, lithium base high temperature inhales a part of lithium in carbon material
Deintercalation enters negative pole, the lithium of consumption required for compensate for the generation of negative pole SEI films, improves the utilization rate of lithium；Multiple cladding is effective
Reduce the Volume Changes in charge and discharge process, reduce the formation of positive electrode micro-crack, at the same effectively barrier positive electrode with
Side reaction occurs for electrolyte, improves the security performance and cycle performance of material.
For the above-mentioned purpose, the present invention uses following technical scheme：
In a first aspect, the present invention, which provides a kind of lithium base high temperature, inhales carbon material modified anode material, the modified anode material
Carbon material is inhaled by positive electrode and lithium base high temperature to form, lithium base high temperature inhales carbon material there are three aspects in the modified anode material
Effect：First, uniform clad anode material forms primary particle, second, the bridge joint primary particle forms second particle, third, equal
The even cladding second particle forms modified anode material.
The lithium base high temperature of the present invention is inhaled in carbon material modified anode material, and lithium base high temperature adsorption material is to positive electrode in more
Layer coated, more particularly：Lithium base high temperature inhales carbon material and is coated on positive electrode surface formation primary particle, coats what is obtained
Primary particle inhales carbon material by lithium base high temperature and bridges to obtain second particle, and lithium base high temperature is inhaled carbon material and is further evenly coated at
The surface of second particle, obtains modified anode material.Covered effect caused by this structure is excellent and electric conductivity is remarkably reinforced,
During carrying out first charge-discharge applied to battery, a part of lithium deintercalation that lithium base high temperature is inhaled in carbon material enters negative pole, makes up
The lithium of consumption required for the generation of negative pole SEI films, the utilization rate of anode material of lithium is effectively increased, is increased with the number of discharge and recharge
Add, crack can increase between positive electrode primary particle, and the multiple cladding that the lithium base high temperature after de- lithium inhales carbon material is effectively reduced
Volume Changes in primary particle charge and discharge process, reduce the formation of positive electrode micro-crack, while effectively obstruct lithium ion
With electrolyte side reaction occurs for the nickelic positive electrode of battery, improves the security performance and cycle performance of material.
Currently preferred technical scheme is used as below, but not as the limitation to technical scheme provided by the invention, is led to
Following preferable technical scheme is crossed, can preferably reach and realize the technical purpose and beneficial effect of the present invention.
Preferably, it is any one in lithium metasilicate, copper acid lithium, lithium zirconate or lithium aluminosilicate that the lithium base high temperature, which inhales carbon material,
Kind or at least two combination, the combination is typical but non-limiting examples have：The combination of lithium metasilicate and copper acid lithium, lithium metasilicate and
The combination of lithium zirconate, the combination of copper acid lithium and lithium aluminosilicate, combination of lithium metasilicate, copper acid lithium and lithium aluminosilicate etc..
Preferably, the chemical composition of the lithium metasilicate is Li4SiO4、Li2SiO3、Li2Si2O5Or Li8SiO6In it is any one
Kind or at least two combination.
Preferably, the chemical composition of the copper acid lithium is Li2CuO2。
Preferably, the chemical composition of the lithium zirconate is Li2ZrO3。
Preferably, the chemical composition of the lithium aluminosilicate is LiAlSi3O8。
Preferably, the positive electrode is tertiary cathode material, preferably ternary layered positive electrode.
Preferably, the chemical composition of the positive electrode is LiaNi1-x-yCoxMnyO2, wherein, 0≤x+y≤1,0.95≤a
≤1.1.The chemical composition of typical but non-limiting positive electrode is Li1.05Ni0.8Co0.1Mn0.1O2、
Li1.00Ni0.6Co0.2Mn0.2O2、Li0.95Ni0.7Co0.15Mn0.15O2And Li1.05Ni0.8Co0.05Mn0.15O2Deng.
Preferably, the second particle is spheric granules.
Preferably, the modified anode material is spheric granules.
Preferably, the median particle diameter of the modified anode material is 3 μm -20 μm, for example, 3 μm, 5 μm, 6 μm, 8 μm, 10 μ
M, 12 μm, 13 μm, 15 μm, 16 μm, 17 μm, 18.5 μm or 20 μm etc., preferably 5 μm -15 μm.
Second aspect, the lithium base high temperature that the present invention provides as described in relation to the first aspect inhale the preparation of carbon material modified anode material
Method, it the described method comprises the following steps：
(1) modified source solution, lithium source solution and positive electrode material precursor are well mixed, are dried to obtain and are inhaled by lithium base high temperature
The homogeneous mixture that carbon materials material precursor is formed with positive electrode material precursor；
Wherein, the modified source solution is any one in silicon source solution, copper source solution, zirconium source solution or silicon and aluminum source solution
Kind or at least two mixture；
(2) homogeneous mixture that step (1) obtains is well mixed with lithium compound, is thermally treated resulting in lithium base high temperature and inhales carbon
Material modification positive electrode.
In the present invention, positive electrode material precursor and modified source solution and lithium source solution are mixed by step (1), this side
Formula can reach the effect being sufficiently impregnated to positive electrode material precursor, and lithium base high temperature suction carbon materials material precursor enters positive pole after drying
Between material precursor particle, not only in the surface uniform fold of positive electrode material precursor primary particle, also bridge in positive pole material
Between material precursor primary particle.Moreover, second particle is combined to form between the primary particle of cladding, lithium base high temperature inhales carbon
Material precursor uniformly coats the second particle.
In the present invention, by step (2) above-mentioned homogeneous mixture and lithium compound in high-temperature sintering process (namely at heat
During reason) react, lithium base high temperature inhales carbon materials material precursor and is changed into lithium base high temperature suction carbon material, positive electrode material precursor
It is changed into positive electrode.In high-temperature sintering process, lithium base high temperature inhales carbon material and gives full play to its suction carbon performance, preferably fully inhales
CO in reaction enclosure atmosphere2, prevent CO2With lithium compound in the ternary layered positive electrode Surface Creation residual carbon of lithium ion battery
Sour lithium, so as to reduce the residual alkali of the ternary layered positive electrode of lithium ion battery.
In the present invention, step (1) the silicon source solution is formulated by silicon source and solvent, and the silicon source preferably includes
Tetraethyl orthosilicate, lithium metasilicate emulsion or Si (OC2H5)4In any one or at least two mixture, but be not limited to
The material enumerated is stated, other silicon sources commonly used in the art can also be used for the present invention.
In the present invention, step (1) copper source solution is formulated by copper source and solvent, and copper source includes nitric acid
The mixture of any one or two kinds in copper or copper chloride, but the above-mentioned material enumerated is not limited to, other are commonly used in the art
Copper source can also be used for the present invention.
In the present invention, step (1) the zirconium source solution is formulated by zirconium source and solvent, and the zirconium source includes nitric acid
The mixture of oxygen zirconium or any one or two kinds in eight hydration zirconium oxychlorides, but the above-mentioned material enumerated is not limited to, other
Zirconium source commonly used in the art can also be used for the present invention.
Preferably, step (1) the silicon and aluminum source solution is the mixed solution being made up of the solution of silicon source and the solution of silicon source,
Or the solution to be formulated by the mixture of silicon source and silicon source and solvent, source of aluminium preferably include aluminum nitrate, hydroxide
In lithium or meta-aluminate any one or at least two mixture.
Preferably, the concentration of the element in the modification source in step (1) the modified source solution is 0.05moL/L-1.5moL/
L, such as 0.05moL/L, 0.1moL/L, 0.15moL/L, 0.2moL/L, 0.3moL/L, 0.5moL/L, 0.7moL/L, 1moL/
L, 1.2moL/L, 1.3moL/L, 1.4moL/L or 1.5moL/L etc..
" element in the modification source in modified source solution " of the present invention refers to：Silicon in the silicon source solution, copper source solution
In copper, the zirconium in the solution of zirconium source, and zirconium and aluminium in silicon and aluminum source solution.
Preferably, step (1) the lithium source solution is any one in lithium nitrate or lithium hydroxide or two kinds of combination.
Preferably, the concentration of the lithium in step (1) the lithium source solution is 0.5mol/L-1mol/L, for example, 0.5mol/
L, 0.6mol/L, 0.7mol/L, 0.75mol/L, 0.8mol/L, 0.85mol/L, 0.9mol/L or 1mol/L etc..
Preferably, step (1) the modified source solution for lithium source solution mass volume ratio for (1g-3g)/
(50mL-200mL), for example, 1g/100mL, 1g/50mL, 1g/200mL, 3g/100mL, 3g/50mL, 3g/200mL, 2g/
60mL, 2g/70mL, 2g/150mL, 2.5g/100mL or 2.5g/200mL etc..
Preferably, step (1) described positive electrode material precursor is ternary anode material precursor, preferably it is ternary layered just
Pole material precursor.
Preferably, the chemical composition of step (1) described positive electrode material precursor is Ni1-x-yCoxMny(OH)2, wherein, 0≤x
+ y≤1, for example, Ni0.8Co0.1Mn0.1(OH)2、Ni0.6Co0.2Mn0.2(OH)2And Ni0.7Co0.15Mn0.15(OH)2Deng.
Preferably, step (1) the modified source solution and the mass ratio of the positive electrode material precursor are (1-3):(50-
200), for example, 1:50、1:60、1:70、1:80、1:100、1:150、1:170、1:180、2:50、2:65、2:85、3:50、3:
70、3:95、3:100、3:160 or 3:200 etc..
Preferably, the gross mass of the homogeneous mixture obtained using step (1) is counted as 100wt%, the positive electrode forerunner
The weight/mass percentage composition of body is more than 90wt%, for example, 90wt%, 91%, 91.5%, 92%, 93%, 93.5%, 94%,
94.5%th, 95%, 95.5%, 96%, 96.5%, 97%, 97.5% or 98% etc..
Preferably, the temperature of step (1) described drying be 120 DEG C -400 DEG C, for example, 120 DEG C, 140 DEG C, 150 DEG C, 160
℃、170℃、185℃、200℃、220℃、230℃、250℃、265℃、280℃、290℃、300℃、315℃、330℃、
340 DEG C, 360 DEG C, 370 DEG C, 380 DEG C, 390 DEG C or 400 DEG C etc..
Preferably, the lithium compound described in step (2) is any in lithium hydroxide, lithium carbonate, lithium nitrate or lithium acetate
It is a kind of or at least two mixture.
Preferably, step (2) it is described it is well mixed by the way of include three-dimensional hybrid, VC mixing or mechanical fusion in
Any one or at least two combination, but be not limited to the above-mentioned hybrid mode enumerated, other can reach well mixed
The hybrid mode of purpose can also be used for the present invention.
Preferably, the temperature of step (2) described heat treatment be 700 DEG C -900 DEG C, for example, 700 DEG C, 725 DEG C, 750 DEG C,
770 DEG C, 800 DEG C, 820 DEG C, 840 DEG C, 850 DEG C, 865 DEG C, 880 DEG C, 890 DEG C or 900 DEG C etc..
Preferably, the time of step (2) described heat treatment is 10h-18h, for example, 10h, 11h, 12h, 13.5h, 15h,
16h, 17h or 18h etc., preferably 12h.
Preferably, step (2) heat treatment is carried out in air atmosphere, oxygen atmosphere or air-oxygen mixed atmosphere,
It is preferred that carried out in oxygen atmosphere.
" air-oxygen mixed atmosphere " of the present invention refers to：The atmosphere being made up of the gaseous mixture of air and oxygen.
Preferably, the lithium base high temperature that step (2) obtains inhales carbon material modified anode material by positive electrode and lithium base high temperature
Carbon material is inhaled to form.
Preferably, the positive electrode is tertiary cathode material, preferably ternary layered positive electrode；
Preferably, the chemical composition of the positive electrode is LiaNi1-x-yCoxMnyO2, wherein, 0≤x+y≤1,0.95≤a
≤1.1。
As the optimal technical scheme of the method for the invention, the described method comprises the following steps：
(1) by any one in silicon source solution, copper source solution, zirconium source solution or silicon and aluminum source solution or at least two it is mixed
Compound, it is well mixed with lithium source and positive electrode material precursor, before 120 DEG C -400 DEG C are dried to obtain and inhale carbon material by lithium base high temperature
Drive the homogeneous mixture that body is formed with positive electrode material precursor；
Wherein, the chemical formula of positive electrode material precursor is Ni1-x-yCoxMny(OH)2, wherein, 0≤x+y≤1；
In the homogeneous mixture, the weight/mass percentage composition of positive electrode material precursor is more than 90wt%；
(2) homogeneous mixture that step (1) obtains is well mixed with lithium compound, in 700 DEG C of -900 DEG C of oxygen atmospheres
Under be heat-treated, obtain lithium base high temperature and inhale carbon material modified anode material, the lithium base high temperature inhales carbon material by positive electrode
And lithium base high temperature is inhaled carbon material and formed, the chemical composition of the positive electrode is LiaNi1-x-yCoxMnyO2, wherein, 0≤x+y≤
1,0.95≤a≤1.1.
The third aspect, the present invention provide a kind of lithium ion battery, and the lithium ion battery includes the lithium described in first aspect
Base high temperature inhales carbon material modified anode material.
Compared with the prior art, the present invention has the advantages that：
The present invention is uniformly mixed by first preparing by lithium base high temperature suction carbon materials material precursor with what positive electrode material precursor was formed
Compound, then it is well mixed with lithium compound, lithium base high temperature is inhaled carbon materials material precursor, positive electrode material precursor and lithium compound
Heat treatment chemically reacts at a certain temperature, and generation lithium base high temperature inhales carbon material modified anode material.What is be prepared changes
Property positive electrode is in multilayer coating structure shape, more particularly：Lithium base high temperature inhales carbon material and is coated on the formation of positive electrode surface once
Particle, the primary particle for coating to obtain inhale carbon material by lithium base high temperature and bridge to obtain second particle, and lithium base high temperature inhales carbon material
The surface of second particle is further evenly coated at, obtains modified anode material.Covered effect caused by this structure it is excellent and
Electric conductivity is remarkably reinforced, and during first charge-discharge is carried out applied to battery, lithium base high temperature inhales a part of lithium in carbon material
Deintercalation enters negative pole, the lithium of consumption required for compensate for the generation of negative pole SEI films, effectively increases the utilization rate of anode material of lithium,
With the number increase of discharge and recharge, crack can increase between positive electrode primary particle, take off the lithium base high temperature after lithium and inhale carbon material
Multiple cladding effectively reduce Volume Changes in primary particle charge and discharge process, reduce the formation of positive electrode micro-crack,
Effectively with electrolyte side reaction occurs for the barrier nickelic positive electrode of lithium ion battery simultaneously, improves the security performance of material and follows
Ring performance.
(2) in method of the invention, carbon materials material precursor is inhaled by lithium base high temperature and mixing that positive electrode material precursor is formed
Thing chemically reacts with lithium compound in heat treatment process, and lithium base high temperature inhales carbon material and gives full play to its suction carbon performance, excellent
Select the CO in abundant adsorption reaction atmosphere2, prevent CO2Given birth to lithium compound on the ternary layered positive electrode surface of lithium ion battery
Into remaining lithium carbonate, so as to reduce the residual alkali of the ternary layered positive electrode of lithium ion battery.
(3) preparation method of the invention is simple, positive effect, easily operation, and reproducible, cost is cheap, and to environment
Pollution it is small, be suitable for industrialized production.
Brief description of the drawings
Fig. 1 is that the lithium base high temperature of embodiment 1 inhales the ternary layered positive electrode of lithium ion battery that carbon material lithium metasilicate is modified
Li1.05Ni0.8Co0.1Mn0.1O2Positive electrode schematic diagram.
Fig. 2 is that the lithium base high temperature of embodiment 1 inhales carbon material lithium metasilicate to the ternary layered positive electrode of lithium ion battery
Li1.05Ni0.8Co0.1Mn0.1O2Positive electrode before modified after cycle life performance curve, wherein, curve after cladding is corresponding real
Apply example 1, the curve before cladding corresponds to comparative example 1.
Fig. 3 is that the lithium base high temperature of embodiment 1 inhales carbon material lithium metasilicate to the ternary layered positive electrode of lithium ion battery
Li1.05Ni0.8Co0.1Mn0.1O2Positive electrode before modified after DSC thermal stability curves, wherein, curve after cladding is corresponding real
Apply example 1, the curve before cladding corresponds to comparative example 1.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Embodiment 1
(1) nitric acid that teos solution, 100mL lithium concentrations that 1g silicon concentrations are 0.5mol/L are 0.5mol/L is weighed
Lithium solution, 100g ternary anode material precursors Ni0.8Co0.1Mn0.1(OH)2Stirred in beaker, 200 DEG C of forced air dryings
Obtain a homogeneous mixture；
(2) thing and monohydrate lithium hydroxide mixed above are weighed, the addition of the two is so that final product (modified positive pole material
Material) in the molar content of each element meet Li1.05Ni0.8Co0.1Mn0.1O2It is defined, mechanical fusion is uniform, at a temperature of 800 DEG C
12h is sintered, lithium base high temperature is obtained and inhales lithium ion battery ternary layered positive electrode (the i.e. lithium base high temperature that carbon material lithium metasilicate is modified
Inhale carbon material modified anode material), the modified anode material is by positive electrode Li1.05Ni0.8Co0.1Mn0.1O2And lithium base high temperature is inhaled
Carbon material lithium metasilicate is formed.
Fig. 1 is that lithium base high temperature inhales the ternary layered positive electrode of lithium ion battery that carbon material lithium metasilicate is modified in the present embodiment
Li1.05Ni0.8Co0.1Mn0.1O2Positive electrode schematic diagram, it is coated on just it will be seen from figure 1 that lithium base high temperature inhales carbon material lithium metasilicate
Pole material surface forms primary particle, and the primary particle for coating to obtain inhales carbon material by lithium base high temperature and bridges to obtain secondary
Grain, lithium base high temperature inhale the surface that carbon material lithium metasilicate is further evenly coated at second particle, obtain modified anode material.
Fig. 2 is that the present embodiment lithium base high temperature inhales carbon material lithium metasilicate to the ternary layered positive electrode of lithium ion battery
Li1.05Ni0.8Co0.1Mn0.1O2Positive electrode before modified after cycle life performance curve, wherein, curve after cladding is corresponding real
Apply example 1, the curve before cladding corresponds to (the i.e. uncoated positive electrode Li of comparative example 11.05Ni0.8Co0.1Mn0.1O2), can be with by figure
To find out, after lithium base high temperature inhales carbon material lithium metasilicate coating modification, 100 weeks capability retentions of 1C/1C charge and discharge cycles improve 5%,
Improve the cycle life of material.
Fig. 3 is that the present embodiment lithium base high temperature inhales carbon material lithium metasilicate to the ternary layered positive electrode of lithium ion battery
Li1.05Ni0.8Co0.1Mn0.1O2Positive electrode before modified after DSC thermal stability curves, wherein, curve after cladding is corresponding real
Apply example 1, the curve before cladding corresponds to (the i.e. uncoated positive electrode Li of comparative example 11.05Ni0.8Co0.1Mn0.1O2), can be with by figure
Find out, lithium base high temperature inhale carbon material lithium metasilicate coating modification after, in material DSC heat stability testing curves exothermic peak temperature from
211.8 DEG C bring up to 230.7 DEG C, and heat endurance and security performance are significantly improved.
Embodiment 2
(1) it is 0.5mol/L to weigh eight hydration zirconyl chloride solutions, 100mL lithium concentrations that 2g zirconium concentration is 0.25mol/L
Lithium hydroxide solution, 100g ternary anode material precursors Ni0.6Co0.2Mn0.2(OH)2Stirred in beaker, 300 DEG C
Forced air drying obtains a homogeneous mixture；
(2) thing and monohydrate lithium hydroxide mixed above are weighed, the addition of the two is so that final product (modified positive pole material
Material) in the molar content of each element meet Li1.1Ni0.6Co0.2Mn0.2O2It is defined, three-dimensional hybrid is uniform, is burnt at a temperature of 900 DEG C
12h is tied, lithium base high temperature is obtained and inhales the ternary layered positive electrode of lithium ion battery (the i.e. lithium base high temperature suction that carbon material lithium zirconate is modified
Carbon material modified anode material), the modified anode material is by positive electrode Li1.1Ni0.6Co0.2Mn0.2O2And lithium base high temperature inhales carbon
Material lithium zirconate is formed.
Embodiment 3
(1) nitric acid that teos solution, 150mL lithium concentrations that 3g silicon concentrations are 0.25mol/L are 1mol/L is weighed
Lithium solution, 80g ternary anode material precursors Ni0.8Co0.1Mn0.1(OH)2Stirred in beaker, 150 DEG C of forced air dryings obtain
To homogeneous mixture；
(2) thing and monohydrate lithium hydroxide mixed above are weighed, the addition of the two is so that final product (modified positive pole material
Material) in the molar content of each element meet Li1.00Ni0.8Co0.1Mn0.1O2It is defined, mechanical fusion is uniform, at a temperature of 820 DEG C
14h is sintered, lithium base high temperature is obtained and inhales lithium ion battery ternary layered positive electrode (the i.e. lithium base high temperature that carbon material lithium metasilicate is modified
Inhale carbon material modified anode material), the modified anode material is by positive electrode Li1.00Ni0.8Co0.1Mnl0.1O2And lithium base high temperature is inhaled
Carbon material lithium metasilicate is formed.
Embodiment 4
(1) nitric acid that teos solution, 200mL lithium concentrations that 2g silicon concentrations are 0.5mol/L are 0.8mol/L is weighed
Lithium solution, 200g ternary anode material precursors Ni0.7Co0.15Mn0.15(OH)2Stirred in beaker, 265 DEG C of forced air dryings
Obtain a homogeneous mixture；
(2) thing and monohydrate lithium hydroxide mixed above are weighed, the addition of the two is so that final product (modified positive pole material
Material) in the molar content of each element meet Li0.95Ni0.7Co0.15Mn0.15O2It is defined, VC is well mixed, at a temperature of 850 DEG C
12h is sintered, lithium base high temperature is obtained and inhales lithium ion battery ternary layered positive electrode (the i.e. lithium base high temperature that carbon material lithium metasilicate is modified
Inhale carbon material modified anode material), the modified anode material is by positive electrode Li0.95Ni0.7Co0.15Mnl0.15O2And lithium base high temperature
Carbon material lithium metasilicate is inhaled to form.
Embodiment 5
(1) it is 0.75mol/ to weigh eight hydration zirconyl chloride solutions, 175mL lithium concentrations that 2.5g zirconium concentration is 1.0mol/L
L lithium hydroxide solution, 120g ternary anode material precursors Ni0.6Co0.2Mn0.2(OH)2Stirred in beaker, 150 DEG C
Forced air drying obtains a homogeneous mixture；
(2) thing and monohydrate lithium hydroxide mixed above are weighed, the addition of the two is so that final product (modified positive pole material
Material) in the molar content of each element meet Li1.00Ni0.6Co0.2Mn0.2O2It is defined, three-dimensional hybrid is uniform, is burnt at a temperature of 880 DEG C
15h is tied, lithium base high temperature is obtained and inhales the ternary layered positive electrode of lithium ion battery (the i.e. lithium base high temperature suction that carbon material lithium zirconate is modified
Carbon material modified anode material), the modified anode material is by positive electrode Li1.00Ni0.6Co0.2Mn0.2O2And lithium base high temperature inhales carbon
Material lithium zirconate is formed.
Comparative example 1
This comparative example 1 is uncoated positive electrode Li1.05Ni0.8Co0.1Mn0.1O2。
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of lithium base high temperature inhales carbon material modified anode material, it is characterised in that the modified anode material is by positive electrode
And lithium base high temperature is inhaled carbon material and formed, the concrete structure of the modified anode material is：Lithium base high temperature inhales carbon material clad anode
Material forms primary particle, the bridge joint primary particle forms second particle, and coats the second particle and form modified positive pole
Material.
2. modified anode material according to claim 1, it is characterised in that it is silicic acid that the lithium base high temperature, which inhales carbon material,
In lithium, copper acid lithium, lithium zirconate or lithium aluminosilicate any one or at least two combination；
Preferably, the chemical composition of the lithium metasilicate is Li4SiO4、Li2SiO3、Li2Si2O5Or Li8SiO6In any one or
At least two combination；
Preferably, the chemical composition of the copper acid lithium is Li2CuO2；
Preferably, the chemical composition of the lithium zirconate is Li2ZrO3；
Preferably, the chemical composition of the lithium aluminosilicate is LiAlSi3O8。
3. modified anode material according to claim 1 or 2, it is characterised in that the positive electrode is tertiary cathode material
Material, preferably ternary layered positive electrode；
Preferably, the chemical composition of the positive electrode is LiaNi1-x-yCoxMnyO2, wherein, 0≤x+y≤1,0.95≤a≤
1.1。
4. according to the modified anode material described in claim any one of 1-3, it is characterised in that the second particle is spherical
Grain；
Preferably, the modified anode material is spheric granules；
Preferably, the median particle diameter of the modified anode material is 3 μm -20 μm, preferably 5 μm -15 μm.
5. the preparation method of the modified anode material as described in claim any one of 1-4, it is characterised in that methods described includes
Following steps：
(1) modified source solution, lithium source solution and positive electrode material precursor are well mixed, are dried to obtain and carbon materials are inhaled by lithium base high temperature
The homogeneous mixture that material precursor is formed with positive electrode material precursor；
Wherein, the modified source solution be silicon source solution, copper source solution, zirconium source solution or silicon and aluminum source solution in any one or
At least two mixture；
(2) homogeneous mixture that step (1) obtains is well mixed with lithium compound, is thermally treated resulting in lithium base high temperature and inhales carbon material
Modified anode material.
6. according to the method for claim 5, it is characterised in that step (1) the silicon source solution is matched somebody with somebody by silicon source and solvent
What system formed, the silicon source includes tetraethyl orthosilicate, lithium metasilicate emulsion or Si (OC2H5)4In any one or at least two
Mixture；
Preferably, step (1) copper source solution is formulated by copper source and solvent, and copper source includes copper nitrate or chlorine
Change the mixture of any one or two kinds in copper；
Preferably, step (1) the zirconium source solution is formulated by zirconium source and solvent, the zirconium source include zirconyl nitrate or
Eight are hydrated the mixture of any one or two kinds in zirconium oxychlorides；
Preferably, step (1) the silicon and aluminum source solution is the mixed solution being made up of the solution of silicon source and the solution of silicon source, or
For the solution being formulated by the mixture of silicon source and silicon source and solvent, source of aluminium preferably include aluminum nitrate, lithium hydroxide or
In meta-aluminate any one or at least two mixture；
Preferably, the silicon in step (1) the silicon source solution, the copper in the solution of copper source, the zirconium in the solution of zirconium source, and silicon and aluminum source
The concentration of zirconium and aluminium in solution independently is 0.05moL/L-1.5moL/L.
7. the method according to claim 5 or 6, it is characterised in that step (1) the lithium source solution is lithium nitrate or hydrogen-oxygen
Change the combination of any one or two kinds in lithium；
Preferably, the concentration of the lithium in step (1) the lithium source solution is 0.5mol/L-1mol/L；
Preferably, step (1) the modified source solution is (1g-3g)/(50mL- for the mass volume ratio of lithium source solution
200mL)；
Preferably, step (1) described positive electrode material precursor is ternary anode material precursor, preferably ternary layered positive pole material
Material precursor；
Preferably, the chemical composition of step (1) described positive electrode material precursor is Ni1-x-yCoxMny(OH)2Wherein, 0≤x+y≤
1；
Preferably, step (1) the modified source solution and the mass ratio of the positive electrode material precursor are (1-3):(50-200)；
Preferably, the gross mass of the homogeneous mixture obtained using step (1) is counted as 100wt%, the positive electrode material precursor
Weight/mass percentage composition is more than 90wt%；
Preferably, the temperature of step (1) described drying is 120 DEG C -400 DEG C.
8. according to the method described in claim any one of 5-7, it is characterised in that the lithium compound described in step (2) is hydrogen-oxygen
Change in lithium, lithium carbonate, lithium nitrate or lithium acetate any one or at least two mixture；
Preferably, step (2) it is described it is well mixed by the way of include three-dimensional hybrid, VC mixing or mechanical fusion in it is any
It is a kind of or at least two combination；
Preferably, the temperature of step (2) described heat treatment is 700 DEG C -900 DEG C；
Preferably, the time of step (2) described heat treatment is 10h-18h, preferably 12h；
Preferably, step (2) heat treatment is carried out in air atmosphere, oxygen atmosphere or air-oxygen mixed atmosphere, preferably
Carried out in oxygen atmosphere；
Preferably, the lithium base high temperature that step (2) obtains inhales carbon material modified anode material and inhales carbon by positive electrode and lithium base high temperature
Material is formed；
Preferably, the positive electrode is tertiary cathode material, preferably ternary layered positive electrode；
Preferably, the chemical composition of the positive electrode is LiaNi1-x-yCoxMnyO2, wherein, 0≤x+y≤1,0.95≤a≤
1.1。
9. according to the method described in claim any one of 5-8, it is characterised in that the described method comprises the following steps：
(1) by any one in silicon source solution, copper source solution, zirconium source solution or silicon and aluminum source solution or at least two mixing
Thing, it is well mixed with lithium source and positive electrode material precursor, is dried to obtain in 120 DEG C -400 DEG C and carbon material forerunner is inhaled by lithium base high temperature
The homogeneous mixture that body is formed with positive electrode material precursor；
Wherein, the chemical formula of positive electrode material precursor is Ni1-x-yCoxMny(OH)2, wherein, 0≤x+y≤1；
In the homogeneous mixture, the weight/mass percentage composition of positive electrode material precursor is more than 90wt%；
(2) homogeneous mixture that step (1) obtains is well mixed with lithium compound, entered under 700 DEG C of -900 DEG C of oxygen atmospheres
Row heat treatment, obtain lithium base high temperature and inhale carbon material modified anode material, the lithium base high temperature inhales carbon material by positive electrode and lithium
Base high temperature is inhaled carbon material and formed, and the chemical composition of the positive electrode is LiaNi1-x-yCoxMnyO2, wherein, 0≤x+y≤1,
0.95≤a≤1.1。
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes changing described in claim any one of 1-4
Property positive electrode.
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