CN101388451A - Lithium cobaltate composite positive pole material and preparation, secondary lithium ionic battery - Google Patents
Lithium cobaltate composite positive pole material and preparation, secondary lithium ionic battery Download PDFInfo
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Abstract
The invention discloses lithium cobalt oxide composite cathode material and a process for preparation thereof, and a secondary lithium ion battery, which aims at solving the technical problem that the cathode material has excellent cycle performance and rate discharge property. The lithium cobalt oxide composite cathode material in the invention uses lithium cobalt oxide granules as basal bodies, and has grain size within 11-16 micron, wherein a lithium manganese oxide coating layer which accounts for 0.5-5% mass ratio of the basal body is coated on the outer side of the basal body. The process for preparation comprises preparing lithium manganese oxide precursors and coating lithium cobalt oxide. The anode of the secondary lithium ion battery is formed by an anode current collector and anode active substances which are coated on the anode current collector, wherein the anode active substance contains lithium cobalt oxide basal body, and the outer side of the basal body is coated with the lithium manganese oxide coating layer which accounts for 0.5-5% mass ratio of the basal body. Compared with the prior art, the cathode material in the invention can manifest excellent cycle performance and rate discharge property, and batteries which are produced through adopting the lithium cobalt oxide material can perform excellent electrochemical performance and higher energy density.
Description
Technical field
The present invention relates to a kind of anode material for lithium ion battery and preparation method thereof, and the lithium ion battery that uses this positive electrode to make, particularly a kind of cobalt acid lithium material and preparation method thereof, and the secondary lithium battery that uses this cobalt acid lithium material to make.
Background technology
Lithium ion battery is since 1991 become commercialized, and its application requirements improves constantly.Its energy density is along with the requirement in market is improving constantly.The energy density of lithium ion battery can be divided into volume energy density and weight energy density specifically, market demand be volume energy density and weight energy density the time improve.Under the prerequisite of same capacity performance, improve the volume of battery energy density, will improve the loading of cell active materials unit volume.For cobalt acid lithium material commonly used, its particle is big more, and then the compacted density of material is big more, and the volume loading of material is just big more, and its volume energy density is just big more.The particle of cobalt acid lithium is brought up to more than 10 microns by initial 5-10 micron and (is measured the number range of its D50 with the laser particle size method) for this reason, and purpose is to improve the loading of active material, and then improves the energy density of battery.But find in the evaluation procedure to oarse-grained cobalt acid lithium material: after particle increased, the electro-chemical activity of positive electrode can reduce, and shows the obvious variation of its cycle performance and multiplying power discharging property.Therefore, can not satisfy the demand of market to the energy density requirement of secondary lithium battery.
Summary of the invention
The purpose of this invention is to provide a kind of cobalt acid lithium composite positive pole and preparation method thereof, secondary lithium battery, the technical problem that solve is a cobalt acid lithium particle more than 10 microns the time, and positive electrode has good cycle performance and multiplying power discharging property.
The present invention is by the following technical solutions: a kind of cobalt acid lithium composite positive pole, has cobalt acid lithium particle, described cobalt acid lithium composite positive pole is a matrix with cobalt acid lithium particle, and granularity is between 11～16 microns, and matrix is coated with and accounts for substrate quality than 0.5～5% LiMn2O4 coating layer.
Matrix cystal of the present invention is a stratiform cobalt acid lithium structure.
Coating layer structure of the present invention is spinelle or layered lithium manganate.
When cobalt acid lithium composite positive pole discharge-rate of the present invention was 0.5～1C, 300 circulation volume conservation rates were greater than 90%.
A kind of preparation method of cobalt acid lithium composite positive pole, may further comprise the steps: one, manganate precursor for lithium preparation: it is in 2～5% the polyacrylamide aqueous colloidal that the lithium salts of elemental lithium content 0.5～1.05mol is scattered in concentration, the manganese salt that adds manganese element content 1.0～2.0mol mixes, drying and dehydrating under 150～450 ℃ of temperature, after the Ball milling with 15～30 ℃ programming rate in 450～600 ℃ of sintering temperatures 5～10 hours, be crushed to granularity about 1 micron, obtain manganate precursor for lithium; Two, cobalt acid lithium coats: with granularity is that 11～16 microns cobalt acid lithium base-material and the manganate precursor for lithium that accounts for its mass ratio 0.5～5% mix, programming rate with 10～20 ℃, at 850～915 ℃ of sintering 10～15 hours, natural cooling, obtain cobalt acid lithium composite positive pole.
Following method is adopted in the preparation of cobalt of the present invention acid lithium matrix: it is in 2～5% the polyacrylamide aqueous colloidal that the lithium salts of elemental lithium content 1.0～1.1mol is scattered in concentration, the cobalt salt that adds cobalt element content 1.0mol then mixes, 350～500 ℃ of dryings, programming rate with 15～30 ℃, 900～920 ℃ of sintering temperatures 15～24 hours, being crushed to granularity was 11～16 microns.
Lithium salts of the present invention is lithium acetate, lithium nitrate or lithium hydroxide; Described cobalt salt is cobalt acetate, cobalt oxalate, cobalt carbonate or cobalt nitrate; Described manganese salt is manganese acetate, manganese oxalate or manganese carbonate.
The mol ratio of lithium of the present invention, manganese element is 1:2.
A kind of secondary lithium battery, has positive pole, described positive pole is made of anode collection device and the positive active material that is coated on the anode collection device, positive active material has cobalt acid lithium matrix, matrix cystal is a stratiform cobalt acid lithium structure, granularity is between 11～16 microns, and matrix is coated with and accounts for substrate quality than 0.5～5% LiMn2O4 coating layer.
The LiMn2O4 coating layer structure of battery of the present invention is spinelle or layered lithium manganate.
The present invention compared with prior art, at cobalt acid lithium surface coating LiMn 2 O, positive electrode can show superior cycle performance and multiplying power discharging property, and the battery table that adopts this cobalt acid lithium material to make reveals the energy density of good electrochemical and Geng Gao.
Description of drawings
Fig. 1 is the stereoscan photograph (3000 times) before embodiment 1 cobalt acid lithium coats.
Fig. 2 is the X-ray diffraction spectrogram before embodiment 1 cobalt acid lithium coats.
Fig. 3 is the stereoscan photograph (10000 times) of embodiment 1 manganate precursor for lithium.
Fig. 4 is the X-ray diffraction spectrogram of embodiment 1 manganate precursor for lithium.
Fig. 5-the 1st, the sem photograph after embodiment 1 cobalt acid lithium coats.
Fig. 5-the 2nd, the heat system after embodiment 1 cobalt acid lithium coats can spectrogram.
Fig. 6 is the X-ray diffraction spectrogram after the cobalt acid lithium of embodiment 1 coats.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.Cobalt acid lithium composite positive pole of the present invention, has cobalt acid lithium matrix, matrix cystal is a stratiform cobalt acid lithium structure, granularity is between 11～16 microns, matrix is coated with and accounts for substrate quality than 0.5～5% LiMn2O4 coating layer, the coating layer structure is spinelle or layered lithium manganate, and this positive electrode compacted density is greater than 3.9g/cm
3, volume energy density is more than the 350Wh/l, and when discharge-rate was 0.5～1C, 300 circulation volume conservation rates were greater than 90%, and the good pole piece of processing characteristics does not come off.
The preparation method of cobalt acid lithium composite positive pole of the present invention may further comprise the steps:
One, cobalt acid lithium base-material preparation: it is in 2～5% polyacrylamide aqueous colloidals that the lithium salts of elemental lithium content 1.0～1.1mol is scattered in concentration, the cobalt salt that adds cobalt element content 1.0mol then mixes, preferred cobalt: elemental lithium mol ratio=1:1.05,350～500 ℃ of drying and dehydratings under air atmosphere, programming rate with 15～30 ℃, 900～920 ℃ of sintering temperatures 15～24 hours, be crushed to particle D then
50Be 11～16 microns, obtaining crystal is the base-material of stratiform cobalt acid lithium structure.Used lithium salts is lithium acetate, lithium nitrate or lithium hydroxide, and used cobalt salt is cobalt acetate, cobalt oxalate, cobalt carbonate or cobalt nitrate.
Two, manganate precursor for lithium preparation: the lithium salts of elemental lithium content 0.5～1.05mol is scattered in the aqueous colloidal that concentration is third rare acid amides of 2～5%, the manganese salt that adds manganese element content 1.0～2.0mol mixes, preferred manganese: elemental lithium mol ratio=1:0.5,150～450 ℃ of drying and dehydratings under air atmosphere, after the Ball milling with 15～30 ℃ programming rate, 450～600 ℃ of sintering temperatures 5～10 hours, pulverized the cooling back naturally, obtains particle D
50Manganate precursor for lithium about 1 micron.Used lithium salts is lithium acetate, lithium nitrate or lithium hydroxide, and used manganese salt is manganese acetate, manganese oxalate or manganese carbonate.
Three, cobalt acid lithium base-material coating LiMn 2 O: with granularity is that 11～16 microns cobalt acid lithium base-material and the manganate precursor for lithium that accounts for cobalt acid lithium material mass ratio 0.5～5% mix, preferred mass ratio is 3.0%, under air atmosphere, programming rate with 10～20 ℃, 860～915 ℃ of sintering 10～15 hours, natural cooling is pulverized the back classification, obtains granularity D
50Cobalt acid lithium composite positive pole at 11～16 microns.
Experimental facilities and instrument that the present invention adopts: dehydration and agglomerating plant: the bright and beautiful stove industry equipment KSF1100-V of Co., Ltd type box type furnace before the Yixing City.Disintegrating apparatus: Lianyun Harbour spring dragon laboratory apparatus SHQM of company type double star ball mill.Classifying equipoment: the TY-200A of Mechanical Equipment Company type standard test sub-sieve is unified in Xinxiang.Analytical instrument: NEC JSM6360 ESEM, the Quanta of Philip FEI Co. 400 thermal field emission scan Electronic Speculum, Japan's lithium is learned D/max-2200pcXRD x ray diffractometer x, Zhuhai American-European gram LS602 laser particle size analyzer, the FZS4-4B of iron and steel research institute type tap density instrument, Pioneer2002 surface measurements instrument.
Secondary lithium battery of the present invention is made of electrode, nonaqueous electrolyte, barrier film and container.Wherein electrode comprises positive pole and negative pole, positive pole is made of anode collection device and the positive active material that is coated on the anode collection device, positive active material has cobalt acid lithium matrix, matrix cystal is a stratiform cobalt acid lithium structure, granularity is between 11～16 microns, matrix is coated with and accounts for substrate quality than 0.5～5% LiMn2O4 coating layer, and the coating layer structure is spinelle or layered lithium manganate.Negative pole is by negative pole currect collecting device and the negative electrode active material layer that is coated on the negative pole currect collecting device.Barrier film is simple solid insulating layer or the decorating film with electric conductivity, is used for positive pole and negative pole are spaced from each other.Container is positive pole, negative pole, barrier film, electrolytical inclusion body.
The cobalt acid lithium composite positive pole of the present invention's preparation is made the secondary lithium-ion Experimental cell.Anodal preparation: the adhesive PVDF of cobalt acid lithium composite positive pole, the conductive carbon black that accounts for positive electrode mass ratio 4% and mass ratio 5% is mixed, ratio in mass ratio 1:1 adds in the N-methyl pyrrolidone, form slurry stirs, be coated on the aluminum foil current collector, drying also is pressed into pole piece.Negative pole preparation: the adhesive PVDF of negative active core-shell material MCMB MCMB, the conductive agent S-P that accounts for negative active core-shell material mass ratio 2% and mass ratio 10% is mixed, ratio in mass ratio 1:1 adds in the N-methyl pyrrolidone, form slurry stirs, be coated on the Copper Foil collector, drying also is pressed into pole piece.Barrier film is the PP material, and container adopts and has the aluminum hull of insulating barrier and the battery cover of lug fairlead.With the positive and negative plate point lug of burn-oning after the compacting, insert barrier film after, in the aluminum hull of packing into after on up-coiler, reeling, with glue the lug fairlead is sealed after lug drawn battery cover.Aluminum hull and battery cover welded seal are in the same place.Inject electrolyte in relative humidity under less than 1.5% environment, electrolyte adopts the mixed solvent of mass ratio EC:DEC:DMC=1:1:1, and electrolyte is the 1M lithium hexafluoro phosphate, seals immediately after the fluid injection.Battery size is a square 053048.
The material that carbon system that negative active core-shell material can also can embed therein and deviate from for lithium ion and non-carbon are, for example Li
4Ti
5O
12, amorphous state tin oxide, WO
2, MoO
2, TiS
2And the carbon that can embed and deviate from lithium ion is thing.Carbon is that thing comprises graphite, non orientation graphite, coke, carbon fiber, spherical carbon, resin sintered carbon, vapor grown carbon and CNT (carbon nano-tube).Show high recharge efficiency because comprise the above-mentioned particular carbon fiber or the negative pole of spherical carbon, special hope uses mesophase pitch-based carbon fibers or the spherical carbon of mesophase pitch base to serve as carbonaceous material.The spherical carbon of mesophase pitch-based carbon fibers and mesophase pitch base can adopt known method to obtain.Nonaqueous electrolyte will be by containing the metal lithium salts LiPF of lithium
6As electrolyte dissolution in the nonaqueous solvents of ethylene carbonate or dimethyl carbonate and obtain.Barrier film does not dissolve in above-mentioned nonaqueous solvents, and is the perforated membrane of being made by polyethylene or acrylic resin, the solid electrolyte that contains the gel electrolyte type that can be obtained by the non-aqueous electrolytic solution plasticized polymeric material yet.Barrier film also can be made by nonwoven fabrics, polyethylene porous membrane or the polypropylene porous film of synthetic resin.
With the charge-discharge test of the secondary lithium-ion Experimental cell of the present invention preparation method of testing, hold up in day BS-9360 of the industrial corporation type battery detecting cabinet in Guangzhou and to carry out according to GB/T18287-2000.
One, cobalt acid lithium matrix preparation: lithium acetate 500g is scattered in the aqueous colloidal of 1000g3% polyethylene glycol, adds the 1300g cobalt oxalate then and stir, 450 ℃ of dryings 5 hours, programming rate with 30 ℃/hour, 905 ℃ of sintering temperatures 18 hours, pulverize the back classification, granularity D
50About 14 microns as cobalt acid lithium base-material.As shown in Figure 1, Scanning Electron Microscope photos reveal powder monocrystalline particle diameter is greater than 13um, and as shown in Figure 2, the analysis of X diffraction pattern has tangible cobalt acid lithium stratiform characteristic peak.
Two, manganate precursor for lithium preparation: lithium acetate 500g is scattered in the aqueous colloidal of 1000g3% third rare acid amides, adding 2600g manganese oxalate salt stirs, at 300 ℃ of following drying and dehydratings, ball milling 2 hours, programming rate with 30 ℃/hour, in 600 ℃ of sintering temperatures 8 hours, pulverized 10 minutes, as precursor used for coating.As shown in Figure 3, Scanning Electron Microscope photos reveal presoma monocrystalline particle diameter is less than 1um, and as shown in Figure 4, X diffraction pattern analysis prompting material does not have complete lattice structure as yet.
Three, cobalt acid lithium coats: cobalt acid lithium base-material and manganate precursor for lithium institute prepared material press mass ratio 1:0.006 mix, with 20 ℃ programming rate, at 850 ℃ of sintering 10 hours, natural cooling, classification after pulverizing obtains granularity D
50It is 13.5 microns cobalt acid lithium composite positive pole.Shown in Fig. 5-1 and Fig. 5-2, this material is carried out the energy spectrum analysis of ESEM heat system, single-crystal surface has obvious coating layer to exist, composition is mainly manganese oxide structure thing, wherein the oxygen element percentage by weight is 22.86% (atomic percent 45.07%), the manganese element percentage by weight is 3.16% (atomic percent 1.81%), and the cobalt element percentage by weight is 67.52% (atomic percent 36.14%).As shown in Figure 6, the X diffractometer shows that this material of lithium cobalt acid structure does not have significant change.
The cobalt acid lithium composite positive pole other technologies parameter that embodiment 1 makes is: specific area 0.30m
2/ g, granularity D
50=13.5um, tap density 2.45g/cm
3
With the cobalt acid lithium composite positive pole of embodiment 1, make the lithium ion battery of 053048 square, then the 0.2C5A capacity of battery is 685 MAHs, and volumetric specific energy is 354Wh/l, and 0.5C～100 capability retentions of 1C circulation are 94.5%.Test data sees Table 1, wherein, and constant current charge ratio=constant current charge capacity/total charging capacity, efficient=discharge capacity/total charging capacity, the cyclic discharge capacity of capacity attenuation rate=discharge capacity/for the third time.
With the cobalt acid lithium composite positive pole of embodiment 2, make the lithium ion battery of 053048 square, then the 0.2C5A capacity of battery is 683 MAHs, and volumetric specific energy is 350Wh/l, and 0.5C～100 capability retentions of 1C circulation are 94.8%.Test data sees Table 2.
With the cobalt acid lithium composite positive pole of embodiment 3, make 053048 square lithium ion battery, then the 0.2C5A capacity of battery is 678 MAHs, and volumetric specific energy is 348 Wh/l, and 0.5C～100 capability retentions of 1C circulation are 95%.Test data sees Table 3.
With the cobalt acid lithium composite positive pole of embodiment 4, make 053048 square lithium ion battery, then the 0.2C5A capacity of battery is 655 MAHs, and volumetric specific energy is 335 Wh/l, and 0.5C～100 capability retentions of 1C circulation are 90.8%.Test data sees Table 4.
Embodiment 5, embodiment 1 cobalt acid lithium base-material and manganate precursor for lithium institute prepared material press 1:0.29 mix, and with 10 ℃ programming rate, 860 ℃ of sintering 12 hours, natural cooling obtained anode material for lithium ion battery and pulverizes classification afterwards, obtains granularity D
50It is 13.9 microns cobalt acid lithium composite positive pole.Other test indexs are: specific area 0.32m
2/ g, granularity D
50=13.9um, tap density 2.50g/cm
3
With the cobalt acid lithium composite positive pole of embodiment 5, make 053048 square lithium ion battery, then the 0.2C5A capacity of battery is 686 MAHs, and volumetric specific energy is 350Wh/l, and 0.5C～100 capability retentions of 1C circulation are 94.8%.Test data sees Table 5.
Embodiment 6, embodiment 1 cobalt acid lithium base-material and manganate precursor for lithium institute prepared material press 1:0.48 mix, and with 15 ℃ programming rate, 915 ℃ of sintering 15 hours, natural cooling obtained anode material for lithium ion battery and pulverizes classification afterwards, obtains granularity D
50It is 14.2 microns cobalt acid lithium composite positive pole.Other test indexs are: specific area 0.29m
2/ g, granularity D
50=14.2um, tap density 2.55g/cm
3
With the cobalt acid lithium composite positive pole of embodiment 6, make 053048 square lithium ion battery, then the 0.2C5A capacity of battery is 675 MAHs, and volumetric specific energy is 345Wh/l, and 0.5C～100 capability retentions of 1C circulation are 93%.Test data sees Table 6.
Comparative Examples 1 is cell active materials, wherein granularity: D with cobalt acid lithium
50Be 7 microns, make 053048 square lithium ion battery, the 0.2C5A capacity of battery is 660 MAHs, and its volumetric specific energy is 339Wh/l, and 0.5C～100 capability retentions of 1C circulation are that 93.5%, 300 circulation volume conservation rate is 88%.
Comparative Examples 2: with cobalt acid lithium is cell active materials, its meso-position radius D
50Be 13 microns, make 053048 square lithium ion battery, the 0.2C5A capacity of battery is 685 MAHs, and its volumetric specific energy is 352Wh/l, and 0.5C～100 capability retentions of 1C circulation are that 88%, 300 circulation volume conservation rate is 75%.
Above-mentioned experimental result shows, increase along with the LiMn2O4 covering amount, cycle performance is able to further raising, capacity descends to some extent simultaneously. therefore, under the prerequisite of content of control LiMn2O4, oarse-grained cobalt acid lithium coated with LiMn2O4 improved the stability of material in cyclic process after handling, prolonged cycle life, because the high compactibility of bulky grain cobalt acid lithium, compacted density is greater than 3.9g/cm
3, the corresponding energy density that improves lithium ion battery satisfies the requirement of the energy density that constantly promotes on the market.
In the embodiments of the invention, lithium salts has only been enumerated lithium acetate, and lithium acetate and lithium nitrate or lithium hydroxide all belong to the capacitive lithium salts, belongs to water soluble compound, can make Co
3+And Li
+Fully the common character of contact works to provide lithium ion in course of reaction of the present invention, so lithium nitrate or lithium hydroxide are suitable for the present invention.Cobalt salt has only been enumerated cobalt oxalate, and cobalt oxalate and cobalt acetate, cobalt carbonate or cobalt nitrate have the common character of divalent cobalt, change Co in course of reaction of the present invention under air atmosphere
3+, provide basic Co-O skeleton, so cobalt acetate, cobalt carbonate or cobalt nitrate are suitable for the present invention.Manganese salt has only been enumerated manganese acetate, and manganese acetate and manganese oxalate or manganese carbonate have the common character of manganous salt, change Mn in course of reaction of the present invention
3+-Mn
4+So manganese oxalate or manganese carbonate are suitable for the present invention.
Claims (10)
1. cobalt acid lithium composite positive pole, has cobalt acid lithium particle, it is characterized in that: described cobalt acid lithium composite positive pole is a matrix with cobalt acid lithium particle, and granularity is between 11～16 microns, and matrix is coated with and accounts for substrate quality than 0.5～5% LiMn2O4 coating layer.
2. cobalt acid lithium composite positive pole according to claim 1 is characterized in that: described matrix cystal is a stratiform cobalt acid lithium structure.
3. cobalt acid lithium composite positive pole according to claim 2, it is characterized in that: described coating layer structure is spinelle or layered lithium manganate.
4. cobalt acid lithium composite positive pole according to claim 3 is characterized in that: when described cobalt acid lithium composite positive pole discharge-rate was 0.5～1C, 300 circulation volume conservation rates were greater than 90%.
5. the preparation method of cobalt acid lithium composite positive pole, may further comprise the steps: one, manganate precursor for lithium preparation: it is in third rare acid amides aqueous colloidal of 2～5% that the lithium salts of elemental lithium content 0.5～1.05mol is scattered in concentration, the manganese salt that adds manganese element content 1.0～2.0mol mixes, drying and dehydrating under 150～450 ℃ of temperature, after the Ball milling with 15～30 ℃ programming rate in 450～600 ℃ of sintering temperatures 5～10 hours, be crushed to granularity about 1 micron, obtain manganate precursor for lithium; Two, cobalt acid lithium coats: with granularity is that 11～16 microns cobalt acid lithium base-material and the manganate precursor for lithium that accounts for its mass ratio 0.5～5% mix, programming rate with 10～20 ℃, at 850～915 ℃ of sintering 10～15 hours, natural cooling, obtain cobalt acid lithium composite positive pole.
6. the preparation method of cobalt acid lithium composite positive pole according to claim 5, it is characterized in that: following method is adopted in the preparation of described cobalt acid lithium matrix: it is in 2～5% the polyacrylamide aqueous colloidal that the lithium salts of elemental lithium content 1.0～1.1mol is scattered in concentration, the cobalt salt that adds cobalt element content 1.0mol then mixes, 350～500 ℃ of dryings, programming rate with 15～30 ℃, 900～920 ℃ of sintering temperatures 15～24 hours, being crushed to granularity was 11～16 microns.
7. the preparation method of cobalt acid lithium composite positive pole according to claim 6, it is characterized in that: described lithium salts is lithium acetate, lithium nitrate or lithium hydroxide; Described cobalt salt is cobalt acetate, cobalt oxalate, cobalt carbonate or cobalt nitrate; Described manganese salt is manganese acetate, manganese oxalate or manganese carbonate.
8. the preparation method of cobalt acid lithium composite positive pole according to claim 7, it is characterized in that: the mol ratio of described lithium, manganese element is 1:2.
9. secondary lithium battery, has positive pole, it is characterized in that: described positive pole is made of anode collection device and the positive active material that is coated on the anode collection device, positive active material has cobalt acid lithium matrix, matrix cystal is a stratiform cobalt acid lithium structure, granularity is between 11～16 microns, and matrix is coated with and accounts for substrate quality than 0.5～5% LiMn2O4 coating layer.
10. secondary lithium battery according to claim 9 is characterized in that: described coating layer structure is spinelle or layered lithium manganate.
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