CN110518229A - A kind of lithium cobaltate cathode material of modification and preparation method thereof - Google Patents
A kind of lithium cobaltate cathode material of modification and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to lithium cobaltate cathode materials of a kind of modification and preparation method thereof, belong to electrode material of lithium battery field, specially first adulterate cobalt acid lithium, the cobalt acid lithium of different-grain diameter is mixed again, finally with the cobalt acid lithium after soft carbon and polyimides coating-doping, lithium cobaltate cathode material obtained is applicable not only to high voltage, with lower internal resistance, and have better electric conductivity and cycle performance, improve the efficiency of first charge-discharge.
Description
Technical field
The present invention relates to lithium cobaltate cathode materials of a kind of modification and preparation method thereof, belong to electrode material of lithium battery neck
Domain.
Background technique
Lithium battery is high with operating voltage, energy density is high, have extended cycle life, is light-weight, self-discharge rate is low, memoryless effect
The advantages that answering is widely used to E-consumer class and other products, therefore lithium battery and its relevant material become scientific research people
The research hotspot of member.Positive electrode is one of lithium battery critical material, decides the performance of lithium battery.With products such as mobile phones
Development requires the volume energy density of battery higher and higher.It is anode with cobalt acid lithium, graphite is that the battery of cathode production occupies
The staple market of battery of mobile phone.In order to improve the energy density of battery, cobalt acid lithium develops toward high voltage direction be trend institute to.
Cobalt acid lithium battery charge cutoff voltage when most starting is 4.2V, and subsequent 4.35V successively occur, the cobalt acid lithium battery of 4.4V, and
And all volume productions, present 4.45V cobalt acid lithium battery also small lot in volume production.But improve the charge cutoff electricity of cobalt acid lithium
After pressure, the lithium that cobalt acid lithium deintercalation comes out is more, and material is more unstable, and cycle performance reduces, deterioration of safety.In order to improve
The stability of material, the method for present mainstream are to be modified processing to cobalt acid lithium using doping and coating technology.
LiCoO2Belong to α-NaFeO2Type structure, space group R-3m, the cubic closest packing based on oxygen atom, Li+And Co3+
It is each located on alternate octahedral site in cubic closest packing, i.e. layer structure is by total side octahedron CoO6It is constituted, during which
It is separated by Li atomic plane.When carrying out charge and discharge, the LiCoO of stratiform2Middle lithium ion is in CoO2The interlayer of atom dense layer carries out two maintenance and operations
Dynamic, as charge cutoff voltage < 4.2V, layer structure is very stable, but in LiCoO2Structure under high stopping potential
Stability is poor.It is primarily due to as charge cutoff voltage > 4.2V, Li1-xCoO2The deintercalation amount x > 0.5 of middle lithium, material hold
Oxygen loss reaction easily occurs, to destroy the stability of structure.To improve LiCoO2Structural stability and thermal safety, commonly
Method of modifying is that it is doped and is coated.With Al, Mg, B, Cu, Cr, Ga, Ti, Zr, P etc. are to LiCoO2Do doping vario-property text
Report is offered it has been shown that suitable doping is optimization LiCoO2Structural stability, improvement lithium ion under positive electrode high voltage
Insertion and abjection characteristic, improve the effective ways of its thermal safety.Such as the doping of Mg element, document " Effect of Mg
doping and MgO-surface modification on the cycling stability of
LiCoO2Electrodes " has the report of this respect.When battery is charged to high pressure, LiCoO2A large amount of Co in structure3+It will become
At Co4+, Co4+Formation will lead to the formation of oxygen defect, this will weaken the binding force between transition metal and oxygen, to make
Co4+It dissolves in electrolyte, in LiCoO2After surface coats nano aluminium oxide, the LiCoO in charge and discharge process2It is aoxidized with nanometer three
The interfacial structure of two aluminium contact will be reset, to reduce the formation of oxygen defect, be correspondingly improved the stable structure of material
Property.If on the other hand material is directly and electrolyte contacts, the Co of strong oxidizing property4+Will react with electrolyte so as to cause
Capacitance loss.It can avoid LiCoO after coated nano-aluminium oxide2It is directly contacted with electrolyte, capacitance loss is reduced, to mention
High LiCoO2The electrochemical specific capacity of material improves its cycle performance, but the cladding of Al element generally causes material resistance
The severe exacerbation of energy.
Summary of the invention
One aspect of the present invention provides a kind of lithium cobaltate cathode material of modification, solves current chemical element Al and directly wraps
After covering cobalt acid lithium, the technical issues of internal resistance penalty, using the lithium cobaltate cathode material after mixture coating-doping, not only have
Standby high blanking voltage, and improve the structural stability and electric conductivity of material.
Another aspect of the present invention additionally provides the preparation method of the lithium cobaltate cathode material of the modification, first adulterates cobalt acid lithium,
The cobalt acid lithium of different-grain diameter is mixed again, finally with the cobalt acid lithium after soft carbon and polyimides coating-doping, cobalt obtained
Sour lithium anode material is applicable not only to high voltage, has lower internal resistance, and have better cycle performance, improves for the first time
The efficiency of charge and discharge.
A kind of lithium cobaltate cathode material of modification is the cobalt acid lithium after soft carbon and polyimides coating-doping.
A kind of preparation method of the lithium cobaltate cathode material of modification, specific steps include:
S1, high temperature solid-state method preparation doping LiCoO2
Lithium source and cobalt source and the compound containing doped chemical are mixed, is roasted after mixing, roasts the material of completion
It is broken to carry out airflow milling again after coarse crushing, obtains the lithium cobaltate cathode material sample of element doping；
The mixing of S2, different-grain diameter lithium cobaltate cathode material
The lithium cobaltate cathode material sample obtained to step S1 carries out Screening Treatment, is 300nm-10 μm for partial size and is classified as
Partial size is 12-20 μm and is classified as bulky grain lithium cobaltate cathode material, by low internal resistance cobalt acid lithium by low internal resistance lithium cobaltate cathode material
Positive electrode is mixed with bulky grain lithium cobaltate cathode material, obtains mixture；
Lithium cobaltate cathode material after S3, soft carbon and polyimides coating-doping
Soft carbon and polyimide powder are mixed with the obtained mixture of step S2, roasted under protective atmosphere
It burns, obtains the low internal resistance lithium cobaltate cathode material of soft carbon and polyimide mixture cladding.
Preferably, lithium source described in step S1 includes one or more of lithium carbonate, lithium hydroxide, lithium acetate, described
Cobalt source include one or more of cobalt oxide, cobalt hydroxide, cobaltous sulfate, cobalt carbonate, cobalt acetate.
Preferably, doped chemical described in step S1 includes Mg, Al, Ti, Zr, Sb, Si, Sn, Mo, one or more of P.
Preferably, in lithium source described in step S1 in the mole and cobalt source of Li element Co element and doped chemical mole
The ratio of the sum of amount is Li:(Co+ doped chemical)=(1.0-1.03): 1.
Preferably, the weight of doped chemical described in step S1 and step S3 ultimately generate the weight of lithium cobaltate cathode material
Than for 0.01-1:100.
Preferably, maturing temperature described in step S1 is 650-1200 DEG C, time 4-24h.
Preferably, the weight that bulky grain lithium cobaltate cathode material described in step S2 is mixed with low internal resistance lithium cobaltate cathode material
Amount is than being 10-2:1.
Preferably, the mass ratio of soft carbon and polyimide powder described in step S3 is 1.5-2.5:1, and soft carbon and polyamides are sub-
The weight ratio that the total weight and step S2 of amine blends obtain mixture is 0.1-1:100.
Preferably, maturing temperature described in step S3 is 600-1200 DEG C, time 10-20h.
The invention has the benefit that
1, doped chemical is mixed with lithium source and cobalt source high temperature, limits specific mole and weight, can optimized
LiCoO2The structural stability of positive electrode, airflow milling is broken again after coarse crushing, and the lithium cobaltate cathode material for controlling preparation exists
In certain particle size range, facilitate the mixing of subsequent big small particle.
2, lithium cobaltate cathode material is divided into different-grain diameter, the large and small partial size of certain weight ratio is mixed, is being considered
On the basis of economic cost, the lithium cobaltate cathode material of low internal resistance can be made, internal resistance performance is better than other cobalts acid in the market
Lithium anode material, compared with the technique for not using large and small partial size cobalt acid lithium mixing, battery performance also improves.
3, LiCoO can be effectively relieved as electronic conduction protective layer in polyimides2Interface heat release with electrolyte is imitated
It answers, the LiCoO under high blanking voltage operating condition2Critically important protective effect is played in battery, but due to polyamides Asia
The increase of amine coating thickness will lead to the reduction of the ionic conductivity and electronic conductivity of positive electrode, and soft carbon is as easy stone
Inkization carbon, due to the characteristic of its structure, electric conductivity is better than LiCoO2, so we use polyimides to be mixed with soft carbon as packet
Coating not only improves the structural stability of positive electrode after cladding, has completely cut off LiCoO2Directly and electrolyte contacts, and have
Better electric conductivity and cycle performance, improve the efficiency of first charge-discharge.
Detailed description of the invention
Fig. 1 be the battery of 1-3 of embodiment of the present invention preparation fill in 0.5C/0.3C puts capacity retention ratio under cycling condition.
Specific embodiment
A kind of preparation method of the lithium cobaltate cathode material of modification, specific steps include:
S1, lithium source and cobalt source and the compound for containing doped chemical (Mg, Al, Ti, Zr, Sb, Si, Sn, Mo, P) are mixed,
Li:(Co+ doped chemical) the ratio of mole be (1.0-1.03): 1, the weight of doped chemical and step S3 ultimately generate cobalt
The weight ratio of sour lithium anode material is 0.01-1:100, is roasted after mixing, and maturing temperature is 650-1200 DEG C, time 4-
For 24 hours, the material for roasting completion carries out airflow milling again after coarse crushing and is crushed, and obtains the lithium cobaltate cathode material sample of element doping；
The lithium source includes one or more of lithium carbonate, lithium hydroxide, lithium acetate, and the cobalt source includes oxidation
One or more of cobalt, cobalt hydroxide, cobaltous sulfate, cobalt carbonate, cobalt acetate.
S2, Screening Treatment is carried out to the lithium cobaltate cathode material sample that step S1 is obtained, is 300nm-10 μm by partial size
It is classified as low internal resistance lithium cobaltate cathode material, partial size is 12-20 μm and is classified as bulky grain lithium cobaltate cathode material, by low internal resistance cobalt
Sour lithium anode material is mixed with bulky grain lithium cobaltate cathode material, bulky grain lithium cobaltate cathode material and low internal resistance lithium cobaltate cathode
The mixed weight ratio of material is 10-2:1, obtains mixture；
S3, soft carbon and polyimide powder are mixed with the obtained mixture of step S2, soft carbon and polyimide powder
The mass ratio at end is 1.5-2.5:1, and the total weight and step S2 of soft carbon and polyimide mixture obtain the weight ratio of mixture
For 0.1-1:100, roasted under protective atmosphere, maturing temperature be 600-1200 DEG C, time 10-20h, obtain soft carbon with
The low internal resistance lithium cobaltate cathode material of polyimide mixture cladding.
Embodiment one:
In lithium, ratio that (cobalt and Mg element) molar ratio is 1.01:1 by lithium carbonate, cobaltosic oxide and magnesia with dry
Method mode mixes in super mixing machine, the lithium cobaltate cathode material that the weight and step S3 of the above modified Mg element ultimately generate
Weight ratio be 0.2%, mixing revolving speed be 2500 revs/min, mixing time be 4 minutes, above-mentioned material is placed in after the completion of mixing
It is roasted 10 hours in roaster with 700 DEG C, the material for roasting completion carries out airflow milling again after coarse crushing and is crushed, and obtains Mg doping
Lithium cobaltate cathode material sample.
Soft carbon and polyimide powder (soft carbon and polyimides matter are carried out to above-mentioned Mg doping lithium cobaltate cathode material sample
Measure than 2:1) mixture cladding, the mixture of sample and soft carbon and polyimide powder is mixed in a certain ratio so that wrap
It covers the 1wt% that mixture accounts for sample and calcines 10h in nitrogen atmosphere at 700 DEG C, obtain mixture cladding cobalt acid lithium sample.
Embodiment two:
In lithium, ratio that (cobalt and Al element) molar ratio is 1.01:1 by lithium carbonate, cobaltosic oxide and aluminium oxide with dry
Method mode mixes in super mixing machine, the weight of the weight of the above Modification on Al element and the lithium cobaltate cathode material ultimately generated
Than being 0.2%, mixing revolving speed is 2500 revs/min, and mixing time is 4 minutes, and above-mentioned material is placed in roaster after the completion of mixing
In roasted 10 hours with 700 DEG C, roasting the material of completion, to carry out airflow milling again after coarse crushing broken, obtains Al doping cobalt acid lithium
Positive electrode sample B screens sample B, is 300nm-10 μm for partial size and is classified as low internal resistance lithium cobaltate cathode material, will be above-mentioned
Partial size is 15-20 μm, is classified as bulky grain lithium cobaltate cathode material.Low internal resistance cobalt acid lithium is mixed with bulky grain lithium cobaltate cathode material
It closes, obtains final mixture N, the blending weight ratio of bulky grain cobalt acid lithium and low internal resistance lithium cobaltate cathode material is 5:1.
The mixture of soft carbon and polyimide powder (soft carbon and polyimides mass ratio 2:1) is carried out to said mixture N
Cladding, mixture N and the mixture of soft carbon and polyimide powder are mixed in a certain ratio, so that cladding mixture accounts for mixing
The 1wt% of object N calcines 10h at 700 DEG C in nitrogen atmosphere, obtain mixture cladding cobalt acid lithium sample.
Embodiment three:
In lithium, ratio that (cobalt and Mg element) molar ratio is 1.01:1 by lithium carbonate, cobaltosic oxide and magnesia with dry
Method mode mixes in super mixing machine, the weight of the weight of the above modified Mg element and the lithium cobaltate cathode material ultimately generated
Than being 0.2%, mixing revolving speed is 2500 revs/min, and mixing time is 4 minutes, and above-mentioned material is placed in roaster after the completion of mixing
In roasted 10 hours with 700 DEG C, roasting the material of completion, to carry out airflow milling again after coarse crushing broken, obtains Mg doping cobalt acid lithium
Positive electrode sample B screens sample B, is 300nm-10 μm for partial size and is classified as low internal resistance lithium cobaltate cathode material, will be above-mentioned
Partial size is 15-20 μm, is classified as bulky grain lithium cobaltate cathode material.Low internal resistance cobalt acid lithium is mixed with bulky grain lithium cobaltate cathode material
It closes, obtains final mixture N, the blending weight ratio of bulky grain cobalt acid lithium and low internal resistance lithium cobaltate cathode material is 6:1.
The mixture of soft carbon and polyimide powder (soft carbon and polyimides mass ratio 2:1) is carried out to said mixture N
Cladding, mixture N and the mixture of soft carbon and polyimide powder are mixed in a certain ratio, so that cladding mixture accounts for mixing
The 1wt% of object N calcines 12h at 800 DEG C in nitrogen atmosphere, obtain mixture cladding cobalt acid lithium sample.
Example IV:
In lithium, (cobalt and Ti element) molar ratio be 1.02:1 ratio by lithium hydroxide, cobalt carbonate and titanium oxide with dry method
Mode mixes in super mixing machine, the weight ratio of the weight of the above modified Ti element and the lithium cobaltate cathode material ultimately generated
It is 0.2%, mixing revolving speed is 2500 revs/min, and mixing time is 4 minutes, and above-mentioned material is placed in roaster after the completion of mixing
It is roasted 8 hours with 800 DEG C, the material for roasting completion carries out airflow milling again after coarse crushing and is crushed, and is obtaining Ti doping cobalt acid lithium just
Pole material sample B screens sample B, is 300nm-10 μm for partial size and is classified as low internal resistance lithium cobaltate cathode material, by above-mentioned grain
Diameter is 15-20 μm, is classified as bulky grain lithium cobaltate cathode material.Low internal resistance cobalt acid lithium is mixed with bulky grain lithium cobaltate cathode material
It closes, obtains final mixture N, the blending weight ratio of bulky grain cobalt acid lithium and low internal resistance lithium cobaltate cathode material is 4:1.
The mixture of soft carbon and polyimide powder (soft carbon and polyimides mass ratio 2:1) is carried out to said mixture N
Cladding, mixture N and the mixture of soft carbon and polyimide powder are mixed in a certain ratio, so that cladding mixture accounts for mixing
The 1wt% of object N calcines 14h at 900 DEG C in nitrogen atmosphere, obtain mixture cladding cobalt acid lithium sample.
Embodiment five:
In lithium, (cobalt and Si element) molar ratio be 1.03:1 ratio by lithium acetate, cobalt hydroxide and silica with dry method
Mode mixes in super mixing machine, the weight of the weight of the above modified Si element and the lithium cobaltate cathode material sample ultimately generated
For amount than being 0.5%, mixing revolving speed is 2500 revs/min, and mixing time is 4 minutes, and above-mentioned material is placed in roasting after the completion of mixing
It is roasted 6 hours in furnace with 900 DEG C, the material for roasting completion carries out airflow milling again after coarse crushing and is crushed, and obtains Si cation doping acid
Lithium anode material sample B screens sample B, is 300nm-10 μm for partial size and is classified as low internal resistance lithium cobaltate cathode material, will be upper
Stating partial size is 15-20 μm, is classified as bulky grain lithium cobaltate cathode material.By low internal resistance cobalt acid lithium and bulky grain lithium cobaltate cathode material
Mixing, obtains final mixture N, and the blending weight ratio of bulky grain cobalt acid lithium and low internal resistance lithium cobaltate cathode material is 3:1.
The mixture of soft carbon and polyimide powder (soft carbon and polyimides mass ratio 2:1) is carried out to said mixture N
Cladding, mixture N and the mixture of soft carbon and polyimide powder are mixed in a certain ratio, so that cladding mixture accounts for mixing
The 1wt% of object N calcines 15h at 1000 DEG C in nitrogen atmosphere, obtain mixture cladding cobalt acid lithium sample.
Embodiment six:
In lithium, (cobalt and Mo element) molar ratio be 1.01:1 ratio by lithium hydroxide, cobaltous sulfate and molybdenum oxide with dry method
Mode mixes in super mixing machine, the weight of the weight of the above modified Mo element and the lithium cobaltate cathode material sample ultimately generated
For amount than being 0.3%, mixing revolving speed is 2500 revs/min, and mixing time is 4 minutes, and above-mentioned material is placed in roasting after the completion of mixing
It is roasted 4 hours in furnace with 1000 DEG C, the material for roasting completion carries out airflow milling again after coarse crushing and is crushed, and obtains Mo cation doping acid
Lithium anode material sample B screens sample B, is 300nm-10 μm for partial size and is classified as low internal resistance lithium cobaltate cathode material, will be upper
Stating partial size is 15-20 μm, is classified as bulky grain lithium cobaltate cathode material.By low internal resistance cobalt acid lithium and bulky grain lithium cobaltate cathode material
Mixing, obtains final mixture N, and the blending weight ratio of bulky grain cobalt acid lithium and low internal resistance lithium cobaltate cathode material is 2:1.
The mixture of soft carbon and polyimide powder (soft carbon and polyimides mass ratio 2:1) is carried out to said mixture N
Cladding, mixture N and the mixture of soft carbon and polyimide powder are mixed in a certain ratio, so that cladding mixture accounts for mixing
The 1wt% of object N calcines 20h at 600 DEG C in nitrogen atmosphere, obtain mixture cladding cobalt acid lithium sample.
Comparative example one:
Difference with embodiment two is:
Mixture N is directly coated with polyimide powder, so that polyimide powder accounts for the 1wt% of mixture N, In
At 700 DEG C, 10h is calcined in nitrogen atmosphere, obtains polyimides cladding cobalt acid lithium sample.
The invention is not limited to above-mentioned specific embodiment, those skilled in the art can also make a variety of variations accordingly,
But it is any all to cover within the scope of the claims with equivalent or similar variation of the invention.
Battery performance test:
Using well known to a person skilled in the art lithium battery preparation and performance test methods, by 1-6 of the embodiment of the present invention and
Lithium cobaltate cathode material made from comparative example 1 is prepared into battery respectively again and is tested for the property: positive electrode LCO:SP:PVDF
It is mixed by the mass ratio of 96.7:1.7:1.6, compacted density 4.15g/cm3, negative electrode material is graphite: CMC:SBR is pressed
The mass ratio of 97.2:1.3:1.5 mixes, compacted density 1.7g/cm3, using the perforated membrane of PP/PE as diaphragm, battery core
Model 376573, electrolyte are the cobalt acid lithium battery electrolyte bought in Yichuan Jin Hui new energy materials Co., Ltd,
Constant current charge-discharge, voltage range 3.0-4.45V are carried out to battery using cell tester.
Figure of description 1 be embodiment 1-3 preparation battery carry out 0.5C fill/0.3C put circulation after capacity retention ratio；
Table 1 is battery performance made from each embodiment and comparative example.
From attached drawing 1 as can be seen that fill in 0.5C/and under 0.3C puts cycling condition, the capacity retention ratio of embodiment 2 and 3 is better than
Embodiment 1, it is seen that technique of the embodiment 2 and 3 using the mixing of large and small partial size cobalt acid lithium, the capacity holding of lithium cobaltate cathode material
Rate is higher, higher than the cycle performance of the lithium cobaltate cathode material of common process preparation.
The battery performance of the lithium cobaltate cathode material of the present invention of table 1 preparation
The battery performance that can be seen that prepared by 2-6 lithium cobaltate cathode material of the embodiment of the present invention from 1 performance data of table is more excellent,
Internal resistance can be down to 36.1m Ω hereinafter, 0.2C gram volume reaches 177.8mAh/g or more, and head fills efficiency up to 92.2% or more, again
Rate (2C/0.2C) is up to 87.3% or more.Compared with the embodiment 1 for not using the mixing of large and small partial size cobalt acid lithium, not only internal resistance compared with
It is low, and other battery performances are also significantly better than embodiment 1；Compared with the comparative example 1 only coated with polyimides, internal resistance difference
Less, the battery performances such as 0.2C gram volume, first charge-discharge efficiency, multiplying power are also more excellent, therefore the large and small partial size cobalt acid of the present invention
Lithium anode material mixing technique, can not only reduce internal resistance, but also battery performance can be improved, at the same using polyimides with
Soft carbon mixture cladding, also optimizes electric conductivity and cycle performance, improves the efficiency of first charge-discharge.
Claims (10)
1. a kind of lithium cobaltate cathode material of modification, it is characterized in that: for the cobalt acid lithium after soft carbon and polyimides coating-doping.
2. a kind of preparation method of the lithium cobaltate cathode material of modification, it is characterized in that: specific steps include:
S1, high temperature solid-state method preparation doping LiCoO2
Lithium source and cobalt source and the compound containing doped chemical are mixed, roasted after mixing, roasts the material of completion through thick
It is broken that airflow milling is carried out after broken again, obtains the lithium cobaltate cathode material sample of element doping；
The mixing of S2, different-grain diameter lithium cobaltate cathode material
The lithium cobaltate cathode material sample obtained to step S1 carries out Screening Treatment, is 300nm-10 μm for partial size and is classified as in low
Lithium cobaltate cathode material is hindered, partial size is 12-20 μm and is classified as bulky grain lithium cobaltate cathode material, by low internal resistance lithium cobaltate cathode
Material is mixed with bulky grain lithium cobaltate cathode material, obtains mixture；
Lithium cobaltate cathode material after S3, soft carbon and polyimides coating-doping
Soft carbon and polyimide powder are mixed with the obtained mixture of step S2, is roasted, is obtained under protective atmosphere
To the low internal resistance lithium cobaltate cathode material of soft carbon and polyimide mixture cladding.
3. a kind of preparation method of the lithium cobaltate cathode material of modification as claimed in claim 2, it is characterized in that: described in step S1
Lithium source include one or more of lithium carbonate, lithium hydroxide, lithium acetate, the cobalt source include cobalt oxide, cobalt hydroxide,
One or more of cobaltous sulfate, cobalt carbonate, cobalt acetate.
4. a kind of preparation method of the lithium cobaltate cathode material of modification as claimed in claim 3, it is characterized in that: described in step S1
Doped chemical include Mg, Al, Ti, Zr, Sb, Si, Sn, Mo, one or more of P.
5. a kind of preparation method of the lithium cobaltate cathode material of modification as described in claim 2-4 any one, it is characterized in that:
The ratio of the sum of mole of Co element and doped chemical is in the mole and cobalt source of Li element in lithium source described in step S1
Li:(Co+ doped chemical)=(1.0-1.03): 1.
6. a kind of preparation method of the lithium cobaltate cathode material of modification as claimed in claim 5, it is characterized in that: described in step S1
Doped chemical weight and step S3 ultimately generate lithium cobaltate cathode material weight ratio be 0.01-1:100.
7. a kind of preparation method of the lithium cobaltate cathode material of modification as claimed in claim 2, it is characterized in that: described in step S1
Maturing temperature be 650-1200 DEG C, time 4-24h.
8. a kind of preparation method of the lithium cobaltate cathode material of modification as claimed in claim 2, it is characterized in that: described in step S2
The weight ratio that is mixed with low internal resistance lithium cobaltate cathode material of bulky grain lithium cobaltate cathode material be 10-2:1.
9. a kind of preparation method of the lithium cobaltate cathode material of modification as claimed in claim 2, it is characterized in that: described in step S3
Soft carbon and the mass ratio of polyimide powder be 1.5-2.5:1, the total weight and step S2 of soft carbon and polyimide mixture
The weight ratio for obtaining mixture is 0.1-1:100.
10. a kind of preparation method of the lithium cobaltate cathode material of modification as described in claim 2 or 9, it is characterized in that: step S3
The maturing temperature is 600-1200 DEG C, time 10-20h.
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