CN106486665A - A kind of low internal resistance lithium cobaltate cathode material and its preparation method and application - Google Patents
A kind of low internal resistance lithium cobaltate cathode material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of low internal resistance lithium cobaltate cathode material and its preparation method and application, this low internal resistance lithium cobaltate cathode material is to be prepared with the little particle cobalt source of 500nm～10 μm particle size range for raw material, final finished is agglomerate morphology, its primary particle size is 200～700nm, 2～10 μm of aggregate particle size, the type cobalt acid lithium sample high comprehensive performance, especially there is low inner resistance, after it carries out a certain proportion of mixing with the monocrystalline cobalt acid lithium sample (as particle diameter is more than 15 μm of cobalt acid lithium) of big particle diameter, the internal resistance of final finished can be significantly improved, simultaneously, the preparation of this low internal resistance lithium cobaltate cathode material also uses and main is mixed with technological means, except its internal resistance performance advantage significantly in addition to, its comprehensive electrochemical properties is also very excellent.Additionally, the inventive method process is simple, it is easy to accomplish industrialized production.
Description
Technical field
The present invention relates to a kind of low internal resistance lithium cobaltate cathode material and its preparation method and application, belong to lithium ion battery battery
Pole Material Field.
Background technology
In the development of cobalt acid lithium material, high voltage is always the application direction of its next step, and in recent years, 4.3V cobalt acid lithium is produced
Product, 4.35V cobalt acid lithium product, 4.4V cobalt acid lithium product all successfully realize commercialization and volume production, are in practical stage, its
In, 4.35V and 4.4V cobalt acid lithium product is application material main at present, additionally, 4.45V material is also in by development
Move towards the process in volume production stage it is contemplated that future should realize successful volume production in 1～2 year, be more than more clearly cobalt acid lithium
The high voltage developing direction of sill, with the rise of the consumer electronics such as smart mobile phone in recent years, for overcoming short etc. asking of continuing a journey
Topic, in addition to the energy density to lithium cobaltate cathode material has most basic raising requirement, it is distinctive right in application link
Low internal resistance, high magnification, quick charge etc. it is also proposed new requirement, and above low internal resistance, high magnification, quick charge etc. are in recent years
Come the new direction of cobalt acid lithium Materials, and be increasingly becoming the new material in addition to this main line of high voltage developing direction
The growth point of research, demand etc. and development branch, comparatively speaking, at present, the development of current consumer electronics cobalt acid lithium sample
On no longer relatively dull, compared to several years ago, market demands of today more three-dimensional, developing direction and the trend with early stage
There occurs obvious difference.
In relatively new material behavior described above, DC internal resistance performance is the important indicator of lithium ion battery, directly
Connect the performance being related to battery in use, the heating that such as high magnification charge/discharge causes and multiplying power property etc., especially
It is accompanied by the release of intelligent mobile class 3C Product and popularization in recent years, above characteristic more proposes higher and higher requirement, and
And be urgent urgent problem, because, in the use requirement of such 3C Product, in safety, in discharge and recharge
Need in journey to reduce battery heat release (the typically no special temperature control system of 3C Product) as far as possible, in computing capability, calculate energy
The high current of power increasingly enhanced CPU, GPU part requirement moment is powered and necessarily the DC internal resistance performance of battery is claimed.
Therefore, the internal resistance reducing battery becomes important improvement direction.Improve currently for cobalt acid lithium material internal resistance aspect of performance
Technological means are concentrated mainly on doping and cladding etc., wherein, the doping of special elementses be improve cobalt acid lithium sample Electron electrical conductivity,
Improve the direct effective ways of cobalt acid lithium material structure stability, the such as doping of Mg element, pertinent literature " Effect of Mg
doping and MgO-surface modification on the cycling stability of
LiCoO2Electrodes " etc. all has report in this respect, and the doping of current Mg element is also to be applied to cobalt acid lithium material to improve
The important method of electronic conductivity, the lithium cobaltate cathode material of main flow all employs the doping of Mg element, has been more ripe
Technological means, and the Surface coating of cobalt acid lithium sample under high voltage condition to reduce material internal resistance have significantly more work
With, such as Patents " Positive active material for rechargeable llithium battery,
Method of preparing the same, and rechargeable lithium battery including the
The same " (patent No.：US 7,687,203 B2) etc. the report that carries out, this is because, under high voltage condition, electrolyte, cobalt acid lithium
Material surface and the contact interface of the two are more active and unstable, have surface coating layer cobalt acid lithium material can effectively by
Cobalt acid lithium material surface and electrolyte are effectively completely cut off, it is to avoid the material internal resistance aspect causing because of side reaction increase sharply and
Destruction of material structure etc., additionally, as Chinese patent " the nonaqueous electrolyte battery " (patent No.：CN1253389 A) report right
Cobalt acid lithium carries out the ionic conductivity that Ti element surface doping etc. can effectively improve cobalt acid lithium material, thus being effectively improved cobalt acid
The internal resistance of lithium material.
But, occur more after the cobalt acid lithium material of above doping, coating technology means and commercialization is combined
Problem, our result of study shows, although bulk doped can be effectively improved the electrical conductivity of material, to improving internal resistance performance
Overall contribution not as good as Surface coating, and in surface coating technology, the cladding of Al element generally causes material internal resistance performance
Severe exacerbation, meanwhile, for ensureing the cycle performance of cobalt acid lithium material, the main flow cobalt acid lithium material under high voltage condition usually must
Must be using more ripe Al cladding.
Content of the invention
For problem above, the lithium cobaltate cathode material for making to have low internal resistance performance quickly and effectively meets main flow cobalt
The commercially use requirement of sour lithium anode material, is necessary for seeking on the basis of normal main flow lithium cobaltate cathode material technological means
Look for the means that can be effectively improved material internal resistance performance and method, for reaching above-mentioned target it is believed that can be in cobalt acid lithium
Particle diameter aspect is targetedly worked because, except above-mentioned the technological means such as be mixed with addition to, the particle diameter of cobalt acid lithium material
It is also the key factor significantly affecting internal resistance performance, the cobalt acid lithium material of big particle diameter has obvious relaxation effect, Li+Embedded
There is obvious hysteresis with abjection, thus leading to material surface to occur to destroy the increase ultimately resulting in material internal resistance, small particle
Cobalt acid lithium material condition under Li+Embedded and abjection relatively easily many, the internal resistance performance of such sample has a clear superiority,
Although single small particle cobalt acid lithium sample is applied to 3C electronic product can have such problems as safety, compacting, can be by
Above-mentioned small particle cobalt acid lithium sample and big particle diameter cobalt acid lithium sample carry out a certain proportion of blending, are effectively reducing material internal resistance
On the basis of performance, it is applied in 3C electronic product.Therefore, preparation has the small particle cobalt acid lithium of obvious internal resistance performance advantage
Sample, by it with normally big particle diameter cobalt acid lithium sample carries out a certain proportion of blending should be just to improve 3C class high voltage cobalt acid lithium
The design direction of pole material.
Therefore, the object of the invention is：A kind of low internal resistance lithium cobaltate cathode material and its preparation method and application, this material are provided
Material not only has significant DCR (Directive Current Resitance, D.C. resistance) performance advantage in itself, and, will
It also can be effectively improved the DCR performance of final finished with bulky grain cobalt acid lithium sample after being blended, additionally, this material combines
Main cobalt acid lithium modification technology means, except DCR performance advantage significantly in addition to, its comprehensive electrochemical properties is also very excellent.
In order to the feature of the present invention is more preferably described, the present invention to implement process as described below.
It is an object of the present invention to provide a kind of low internal resistance lithium cobaltate cathode material, this low internal resistance lithium cobaltate cathode material
To the body of lithium cobaltate cathode material and finished product obtained from modifying surface by modifying element, modifying element be selected from Mg,
One or more of Ti, Al, Zr, Sn, Zn, Ca, modifying element with the weight ratio of low internal resistance lithium cobaltate cathode material finished product is
0.01%～1%, this low internal resistance lithium cobaltate cathode material finished product is agglomerate morphology, and its primary particle size is 200～700nm, two
Secondary particle diameter is 2～10 μm.
Another object of the present invention is to provide a kind of preparation method of low internal resistance lithium cobaltate cathode material, the method bag
Include following steps：
1) by lithium source and cobalt source and the mixing of the compound containing modifying element M, the mole of Li element and cobalt source in lithium source
The ratio of the mole sum of middle Co element and modifying element M is Li:(Co+M)=(1.0～1.02):1, the weight of modifying element M
Amount with ultimately generate the weight of cobalt acid lithium material ratio for 0.01%～1%；
2) by step 1), in 600～1100 DEG C of roastings 6～20 hours, the material that roasting completes is through thick for the material that is mixed to get
Carry out airflow milling after broken again to crush, obtain low internal resistance lithium cobaltate cathode material.
Further, step 1) in cobalt source include one of cobalt oxide, cobalt hydroxide and cobalt carbonate, cobaltous acetate or several
Kind.
Further, step 1) in cobalt source particle diameter be 500nm～10 μm, that is, using compared with small particle cobalt source, be nanoscale
Little particle cobalt source or 2～3 μm of monocrystalline type little particle cobalt source, or spherical little particle cobalt source.
Further, step 1) in lithium source include one or more of lithium carbonate, Lithium hydrate and lithium acetate.
Further, step 1) in cobalt source and lithium source and the mixed process of compound containing modifying element M using batch mixing
The preferably super mixer of dispersibility is carried out, and controls rotating speed to be 1000～2700 revs/min, mixing time controls at 2～6 points
Clock.
Further, step 2) in, the primary particle size of the low internal resistance lithium cobaltate cathode material obtaining is 200～700nm, two
Secondary particle diameter is 2～10 μm.
It is a further object to provide a kind of low internal resistance lithium cobaltate cathode material answering on improving DCR performance
With carrying out cladding after blend low internal resistance lithium cobaltate cathode material with bulky grain cobalt acid lithium and realizing.
Further, the particle diameter of above-mentioned bulky grain cobalt acid lithium is 12～20 μm, preferably 15～20 μm.
Further, bulky grain cobalt acid lithium and the blending part by weight of low internal resistance lithium cobaltate cathode material are 10:1～1:1,
Preferably 8:1～4:1.
Further, the method being coated after above-mentioned blending is dry method cladding or wet method cladding.
Further, dry method cladding is main includes：
1 1) add the chemical combination containing modifying element after bulky grain cobalt acid lithium being mixed with low internal resistance lithium cobaltate cathode material
To carry out material modification, the doping weight of above modifying element and the ratio of cobalt acid lithium total weight of the mixture are 0.01%～1% to thing；
1 2) by step 1-2) material that obtains is sintered, and sintering temperature controls at 400 DEG C～1000 DEG C, preferably
700 DEG C～980 DEG C, sintering time controlled at 5～12 hours.
Further, step 1-1) in mixed using super mixer, control rotating speed be 1000～2700 revs/min
Clock, incorporation time controlled at 2～6 minutes.
Further, step 1-1) in the compound containing modifying element can be Mg, Ti, Al, Zr, Sn, Zn, Ca element
Metal-oxide, one or more of all metal inorganic compounds such as metal hydroxidess, and particle size is and receives
Meter level.
Further, wet method cladding is main includes：
2 1) big particle diameter cobalt acid lithium and low internal resistance lithium cobaltate cathode material are mixed to get cobalt acid lithium mixture, and will contain
The compound of modifying element is configured to colloidal sol, the doping weight of above modifying element and cobalt acid lithium total weight of the mixture in ethanol
Ratio be 0.01%～1%；
2 2) by step 2-1) in cobalt acid lithium mixture be dispersed in colloidal sol, stirring 1～4 hour after, dry, burn
Knot process, drying temperature controls at 80～200 DEG C, and drying time controls at 2～6 hours, sintering temperature control 400 DEG C～
1000 DEG C, preferably 700 DEG C～980 DEG C, sintering time controlled at 5～12 hours.
Further, step 2-1) in the compound containing modifying element can be Mg, Ti, Al, Zr, Sn, Zn, Ca element
Metal alkoxide, metal ester salt, metal nitrate, in all metallo-organic compounds such as metal sulfate or metal acetate salt
One or more, preferably metal alkoxide, metal ester salt.
Advantages of the present invention is as follows：
1., present invention is generally directed to small particle cobalt acid lithium sample has carried out the design of grain size aspect, it is prepared for once grain
Footpath about 200～700nm, a kind of low internal resistance lithium cobaltate cathode material of about 2～10 μm of aggregate particle size, meanwhile, its body and surface
Carry out the modification of metallic element Mg, Ti, Al, Zr, Zn, Sn, Ca etc., this material has significant advantage in internal resistance performance, with
Normally big particle diameter cobalt acid lithium sample carries out the finished product internal resistance performance after certain proportion blending and is substantially better than similar cobalt acid lithium sample,
Additionally, the present invention has taken into full account the technological means of normal commercial main flow lithium cobaltate cathode material, it is combined with above technology
The improvement project being effectively improved material internal resistance on the basis of means, therefore, in addition to internal resistance performance advantage is fairly obvious, this is low interior
Resistance lithium cobaltate cathode material also remains the capacity that main cobalt acid lithium modification technology means are brought, efficiency, platform, multiplying power, follows
The good advantageous feature of the combination properties such as ring performance.
2. operating process of the present invention is easy, and the cost of raw material is relatively low, it is easy to accomplish industrialized production.
Brief description
Fig. 1 is the SEM figure of the low internal resistance cobalt acid lithium sample in embodiment three.
Fig. 2 is the XRD figure of the low internal resistance cobalt acid lithium sample in embodiment three.
Fig. 3 is the SEM figure of the blending finished product in embodiment three.
Fig. 4 is the SEM figure of the blending finished product in comparative example.
Fig. 5 is blending 25 DEG C of finished product in embodiment three, charge and discharge under the conditions of 3.0～4.6V button cell, 0.7C multiplying power
The cycle performance figure of electricity.
Specific embodiment
Embodiment one
(1) press lithium, (cobalt and Mg element) mol ratio is 1:1 ratio is by lithium carbonate, 10 μm of Cobalto-cobaltic oxides and magnesium oxide
Mixed in super mixer in dry method mode, the above modification weight of Mg element and the little particle cobalt acid lithium sample ultimately generating
Weight ratio for 0.01%, batch mixing rotating speed is 2700 revs/min, and mixing time is 3 minutes, after the completion of mixing is placed in above-mentioned material
With 600 DEG C of roastings 10 hours in roaster, the material that roasting completes carries out airflow milling after coarse crushing again and crushes, and finally gives and treats
The primary particle size about 300nm of cladding, the little particle cobalt acid lithium sample of about 10 μm of aggregate particle size.
(2) by the little particle cobalt acid lithium sample obtaining in 15 μm of bulky grain cobalt acid lithium sample and (1) with 6:1 ratio is entered
Row mixing, and add nano level magnesium oxide, titanium dioxide, aluminium oxide, Mei Zhonggai in this size particles cobalt acid lithium mixture
Property the weight of element be 0.01% with the ratio of the gross weight of size particles cobalt acid lithium mixture, mixed process use super mixing
Machine is carried out, batch mixing rotating speed be 1000 revs/min, mixing time be 2 minutes, after the completion of mixing by above-mentioned material be placed in roaster with
400 DEG C of roastings 5 hours, the material that roasting completes sieves process after coarse crushing, finally gives the black powder with low DCR performance
Last shape cobalt acid lithium material.
Embodiment two
(1) press lithium, (cobalt and Al element) mol ratio is 1.005:1 ratio is by Lithium hydrate, 3 μm of cobalt hydroxides and nanometer
Aluminium oxide is mixed in super mixer in dry method mode, and the weight of above Modification on Al element and the small particles of cobalt ultimately generating are sour
For 0.1%, batch mixing rotating speed is 1500 revs/min to the weight of lithium sample ratio, and mixing time is 4 minutes, by above-mentioned thing after the completion of mixing
Material is placed in 1000 DEG C of roastings 10 hours in roaster, and the material that roasting completes carries out airflow milling after coarse crushing again and crushes,
Obtain primary particle size to be covered about 500nm, the little particle cobalt acid lithium sample of about 5 μm of aggregate particle size eventually.
(2) by the little particle cobalt acid lithium sample obtaining in 17 μm of bulky grain cobalt acid lithium sample and (1) with 7:1 ratio is entered
Row mixing, and add in this size particles cobalt acid lithium mixture nano level magnesium oxide, titanium dioxide, aluminium oxide, zirconium oxide,
Stannum oxide, the gross weight of every kind of modifying element is 0.1% with the ratio of the gross weight of size particles mixture, and mixed process uses
Super mixer is carried out, and batch mixing rotating speed is 2000 revs/min, and mixing time is 4 minutes, after the completion of mixing, above-mentioned material is placed in roasting
Burn in stove with 970 DEG C of roastings 8 hours, the material that roasting completes sieves process after coarse crushing, finally gives and has low DCR performance
Black powder cobalt acid lithium material.
Embodiment three
(1) press lithium, (cobalt and Mg, Ti element) mol ratio is 1.001:1 ratio by lithium carbonate, 3.5 μm of Cobalto-cobaltic oxides,
Magnesium oxide, titanium dioxide are mixed in super mixer in dry method mode, the weight of above every kind of modifying element with ultimately generate
The weight ratio of little particle cobalt acid lithium sample be 0.15%, batch mixing rotating speed is 1800 revs/min, and mixing time is 4 minutes, mixing
After the completion of above-mentioned material is placed in 1015 DEG C of roastings 10 hours in roaster, the material that roasting completes is carried out after coarse crushing again
Airflow milling crushes, and finally gives little particle cobalt acid lithium sample to be covered, as shown in figure 1, can be seen that sample by this SEM figure
About 4 μm of primary particle size about 700nm, aggregate particle size, and essentially reunion pattern, show, sample presents according to the XRD spectra of Fig. 2
The characteristic peak of typical cobalt acid lithium.
(2) by the little particle cobalt acid lithium sample obtaining in 18 μm of bulky grain cobalt acid lithium sample and (1) with 8:1 ratio is entered
Row mixing, and add in this size particles cobalt acid lithium mixture nano level magnesium oxide, titanium dioxide, aluminium oxide, zinc oxide,
Calcium oxide, the gross weight of this modifying element is 1% with the ratio of the gross weight of size particles mixture, and mixed process uses super mixed
Conjunction machine is carried out, and batch mixing rotating speed is 2700 revs/min, and mixing time is 6 minutes, after the completion of mixing, above-mentioned material is placed in roaster
With 1000 DEG C of roastings 12 hours, the material that roasting completes sieved process after coarse crushing, finally gives and has the black of low DCR performance
Color powder cobalt acid lithium material, is shown in Fig. 3, and the SEM in figure of this blending finished product shows, after blending, compared with bulky grain cobalt acid lithium, little
The particle diameter of granule cobalt acid lithium is less, and the size particles of this type blend the characteristic that form has relatively low internal resistance.
The 4.6V normal-temperature circulating performance of this sample is shown in accompanying drawing 5, and the cycle performance of sample is more excellent, and capability retention is permissible within 50 weeks
Reach 92% about.
Example IV
(1) press lithium, (cobalt and Mg, Zr, Sn, Zn, Ca element) mol ratio is 1.02:1 ratio is by lithium acetate, 500nm carbon
Sour cobalt, magnesium oxide, zirconium oxide, stannum oxide, zinc oxide, calcium oxide is mixed in super mixer in dry method mode, above every kind of
The weight of modifying element is 1% with the weight ratio of the little particle cobalt acid lithium sample ultimately generating, batch mixing rotating speed be 1800 turns/
Point, mixing time is 4 minutes, after the completion of mixing, above-mentioned material is placed in 1015 DEG C of roastings 10 hours in roaster, roasting is complete
The material becoming carries out airflow milling after coarse crushing again and crushes, and finally gives primary particle size to be covered about 200nm, aggregate particle size is about
2 μm of little particle cobalt acid lithium sample.
(2) by the little particle cobalt acid lithium sample obtaining in 12 μm of bulky grain cobalt acid lithium sample and (1) with 10:1 ratio
Carry out being mixed to get size particles cobalt acid lithium mixture, wet method cladding is carried out to this mixture, detailed process is：First by nitric acid
Magnesium, butyl titanate, aluminum isopropylate. are dispersed in the colloidal sol obtaining above modified metal element in ethanol, above-mentioned modified metal
The gross weight of element is 0.01% with the ratio of the gross weight of size particles cobalt acid lithium mixture, by size particles cobalt after the completion of dispersion
Sour lithium mixture is added in this ethanol colloidal sol, and ethanol was evaporated after 1 hour by stirring, and the material being evaporated is carried out at 80 DEG C of drying
Reason, drying time controls at 6 hours, is placed in 400 DEG C of roastings 5 hours in roaster by above-mentioned material after the completion of drying and processing,
The material that roasting completes sieves process after coarse crushing, finally gives the black powder cobalt acid lithium material with low DCR performance.
Embodiment five
(1) press lithium, (cobalt and Ti element) mol ratio is 1.015:1 ratio is by lithium carbonate, 4 μm of Cobalto-cobaltic oxides and dioxy
Change titanium mix in super mixer in dry method mode, the weight of above modified Ti element and the little particle cobalt acid lithium ultimately generating
For 0.15%, batch mixing rotating speed is 2000 revs/min to the weight of sample ratio, and mixing time is 6 minutes, by above-mentioned material after the completion of mixing
It is placed in 1020 DEG C of roastings 20 hours in roaster, the material that roasting completes carries out airflow milling after coarse crushing again and crushes, finally
Obtain primary particle size to be covered about 500nm, the little particle cobalt acid lithium sample of about 4 μm of aggregate particle size.
(2) by the little particle cobalt acid lithium sample obtaining in 20 μm of bulky grain cobalt acid lithium sample and (1) with 1:1 ratio is entered
Row is mixed to get size particles cobalt acid lithium mixture, carries out wet method cladding to this mixture, detailed process is：First by nitric acid
Magnesium, butyl titanate, aluminum isopropylate., tetrabutyl zirconate are dispersed in the colloidal sol obtaining above modified metal element in ethanol,
The gross weight of above-mentioned modified metal element is 1% with the ratio of the gross weight of size particles cobalt acid lithium mixture, will after the completion of dispersion
Size particles cobalt acid lithium mixed material is added in this ethanol colloidal sol, and ethanol was evaporated after 4 hours by stirring, and the material being evaporated is entered
200 DEG C of drying and processings of row, drying time controls at 2 hours, after the completion of drying and processing by above-mentioned material be placed in roaster with
1000 DEG C of roastings 12 hours, the material that roasting completes sieves process after coarse crushing, finally gives the black with low DCR performance
Powder cobalt acid lithium material.
Embodiment six
(1) press lithium, (cobalt and Ti element) mol ratio is 1.015:1 ratio is by lithium carbonate, 3 μm of cobaltous acetate and titanium dioxide
Mixed in super mixer in dry method mode, the above modification weight of Ti element and the little particle cobalt acid lithium sample ultimately generating
Weight ratio for 0.05%, batch mixing rotating speed is 2000 revs/min, and mixing time is 5 minutes, after the completion of mixing is placed in above-mentioned material
With 1020 DEG C of roastings 15 hours in roaster, the material that roasting completes carries out airflow milling after coarse crushing again and crushes, and finally gives
Primary particle size to be covered about 400nm, the little particle cobalt acid lithium sample of about 4 μm of aggregate particle size.
(2) by the little particle cobalt acid lithium sample obtaining in 18 μm of bulky grain cobalt acid lithium sample and (1) with 1:1 ratio is entered
Row is mixed to get size particles cobalt acid lithium mixture, carries out wet method cladding to this mixture, detailed process is：First by nitric acid
Magnesium, butyl titanate, aluminum isopropylate., tetrabutyl zirconate are dispersed in the colloidal sol obtaining above modified metal element in ethanol,
The gross weight of above-mentioned modified metal element is 1% with the ratio of the gross weight of size particles cobalt acid lithium mixture, will after the completion of dispersion
Size particles cobalt acid lithium mixed material is added in this ethanol colloidal sol, and ethanol was evaporated after 4 hours by stirring, and the material being evaporated is entered
200 DEG C of drying and processings of row, drying time controls at 2 hours, after the completion of drying and processing by above-mentioned material be placed in roaster with
1000 DEG C of roastings 12 hours, the material that roasting completes sieves process after coarse crushing, finally gives the black with low DCR performance
Powder cobalt acid lithium material.
It should be noted that enumerated above is only the specific embodiment of the present invention it is clear that the invention is not restricted to above
Embodiment, any some modifications and changes to this invention all should fall within the scope of the claims of the present invention.
Comparative example
This comparative example is not related to the preparation of low internal resistance cobalt acid lithium sample, and other conditions are then consistent with above-mentioned 6 embodiments.This
The preparation method of the cobalt acid lithium material of comparative example is as follows：
(1) press lithium, cobalt mol ratio is 1.001:1 ratio by lithium carbonate, Cobalto-cobaltic oxide with dry method mode ball milling mixing,
After the completion of mixing, above-mentioned material is placed in 1020 DEG C of roastings 10 hours in roaster, the material that roasting completes after coarse crushing again
Carry out airflow milling to crush, finally give about 2 μm of primary particle size to be covered, the little particle cobalt acid lithium sample of about 9 μm of aggregate particle size.
(2) by the little particle cobalt acid lithium sample obtaining in 17 μm of bulky grain cobalt acid lithium sample and (1) with 1:1 ratio is entered
Row is mixed to get size particles cobalt acid lithium mixture, carries out wet method cladding to this mixture, detailed process is：First by nitric acid
Magnesium, butyl titanate, aluminum isopropylate., tetrabutyl zirconate are dispersed in the colloidal sol obtaining above modified metal element in ethanol,
The weight of above-mentioned every kind of modified metal element and the ratio of the gross weight of size particles cobalt acid lithium mixture are 1%, and dispersion completes
Afterwards size particles cobalt acid lithium mixture is added in this ethanol colloidal sol, ethanol was evaporated, by the material being evaporated after 4 hours by stirring
Carry out 200 DEG C of drying and processings, drying time controls at 2 hours, after the completion of drying and processing by above-mentioned material be placed in roaster with
1000 DEG C of roastings 12 hours, the material that roasting completes sieves process after coarse crushing, finally gives the black with low DCR performance
Powder cobalt acid lithium material, is shown in Fig. 4, and the SEM figure of this blending finished product shows, the little particle in this blending finished product and low internal resistance sample
Compare, either primary particle size or aggregate particle size all have obvious increasing compared with the low internal resistance small particles of cobalt acid lithium material of the present invention
Plus, accordingly, the internal resistance of the cobalt acid lithium material of this type is higher.
The primary particle size of low internal resistance cobalt acid lithium sample in each embodiment, aggregate particle size, pH and SSA analysis
To in above-described embodiment and comparative example preparation low internal resistance cobalt acid lithium sample carried out primary particle size, aggregate particle size,
The test of pH and SSA, as shown in table 1.
The primary particle size of low internal resistance cobalt acid lithium sample in each embodiment of table 1 and comparative example, aggregate particle size, pH and SSA
Test result
Test result shows, is the small particles of cobalt that primary particle size is nano level ultra-small grain size in embodiment one to six
Sour lithium sample, the primary particle size of comparative example small particles cobalt acid lithium sample is micron order, in addition, pH the and SSA data from table 1
On can see, ultra-small grain size cobalt acid lithium sample all has relatively low pH value, and its surface residual Li amount is less, the acid of the cobalt of this type
Lithium sample has preferably electrical property, and meanwhile, the specific surface of low internal resistance cobalt acid lithium sample is all larger.
Size particles in each embodiment blend the DCR performance evaluation of finished product
The size particles of above-described embodiment and comparative example are blended with finished product and has carried out 3.0～4.4V using button cell, 25
The DCR performance test of DEG C condition, as shown in table 2.
Size particles in each embodiment of table 2 and comparative example blend the DCR value (3.0～4.4V) at finished product difference SOC
Test result shows, after the blending of this ultra-small grain size cobalt acid lithium sample, the final DCR performance blending finished product is relatively
Sample in comparative example has and is obviously improved, the DCR value at especially 10%SOC.
Claims (10)
1. a kind of low internal resistance lithium cobaltate cathode material, this low internal resistance lithium cobaltate cathode material is to lithium cobaltate cathode by modifying element
Finished product obtained from the body of material and modifying surface, described modifying element is selected from Mg, Ti, Al, Zr, Sn, Zn, Ca
One or more, the weight of described modifying element and low internal resistance lithium cobaltate cathode material finished product is than for 0.01%～1%, described low
Internal resistance lithium cobaltate cathode material finished product is agglomerate morphology, and its primary particle size is 200～700nm, and aggregate particle size is 2～10 μm.
2. a kind of preparation method of low internal resistance lithium cobaltate cathode material, the method comprises the following steps：
1) by lithium source and cobalt source and the mixing of the compound containing modifying element M, the mole of Li element and Co in cobalt source in lithium source
The ratio of the mole sum of element and modifying element M is Li:(Co+M)=(1.0～1.02):1, the weight of modifying element M with
Ultimately generate the weight of cobalt acid lithium material than for 0.01%～1%；
2) by step 1), in 600～1100 DEG C of roastings 6～20 hours, the material that roasting completes is through coarse crushing for the material that is mixed to get
Carry out airflow milling afterwards again to crush, obtain low internal resistance lithium cobaltate cathode material.
3. as claimed in claim 2 the preparation method of low internal resistance lithium cobaltate cathode material it is characterised in that step 1) in, institute
State cobalt source and include one or more of cobalt oxide, cobalt hydroxide and cobalt carbonate, cobaltous acetate, cobalt source particle diameter is 500nm～10 μm.
4. as claimed in claim 2 the preparation method of low internal resistance lithium cobaltate cathode material it is characterised in that step 1) in, institute
State lithium source and include one or more of lithium carbonate, Lithium hydrate and lithium acetate.
5. as claimed in claim 2 the preparation method of low internal resistance lithium cobaltate cathode material it is characterised in that step 1) in, institute
State modifying element M and be selected from one or more of Mg, Ti, Al, Zr, Sn, Zn, Ca.
6. as claimed in claim 2 the preparation method of low internal resistance lithium cobaltate cathode material it is characterised in that step 1) in, institute
State cobalt source and lithium source and the compound containing modifying element M mixed using super mixer, mixing rotating speed be 1000～
2700 revs/min, mixing time 2～6 minutes.
7. application on improving DCR performance for the low internal resistance lithium cobaltate cathode material described in claim 1, by will be described low interior
Carry out cladding realization after resistance lithium cobaltate cathode material and the blending of bulky grain cobalt acid lithium.
8. as claimed in claim 7 application on improving DCR performance for the low internal resistance lithium cobaltate cathode material it is characterised in that
The particle diameter of described bulky grain cobalt acid lithium is 12～20 μm.
9. as claimed in claim 7 application on improving DCR performance for the low internal resistance lithium cobaltate cathode material it is characterised in that
Described bulky grain cobalt acid lithium is 10 with the blending part by weight of described low internal resistance lithium cobaltate cathode material:1～1:1.
10. as claimed in claim 7 application on improving DCR performance for the low internal resistance lithium cobaltate cathode material it is characterised in that
The method being coated after blending is dry method cladding or wet method cladding.
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| CN113511690A (en) * | 2021-07-16 | 2021-10-19 | 北京泰丰先行新能源科技有限公司 | Preparation method of uniformly aluminum-doped large and small particle cobaltosic oxide and positive electrode material |
| CN114220945A (en) * | 2021-12-14 | 2022-03-22 | 天津巴莫科技有限责任公司 | High-compaction lithium cobalt oxide positive electrode material with bimodal distribution and preparation method thereof |
| CN114220945B (en) * | 2021-12-14 | 2024-05-31 | 天津巴莫科技有限责任公司 | High-compaction lithium cobalt oxide positive electrode material with bimodal distribution and preparation method thereof |
| CN114790012A (en) * | 2022-04-22 | 2022-07-26 | 格林美（无锡）能源材料有限公司 | Lithium cobaltate positive electrode material and preparation method and application thereof |
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