CN103094550B - Preparation method of lithium-rich anode material - Google Patents
Preparation method of lithium-rich anode material Download PDFInfo
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- CN103094550B CN103094550B CN201110337732.6A CN201110337732A CN103094550B CN 103094550 B CN103094550 B CN 103094550B CN 201110337732 A CN201110337732 A CN 201110337732A CN 103094550 B CN103094550 B CN 103094550B
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Abstract
The invention discloses a preparation method of a lithium-rich anode material having a chemical formula of xLi2O.yMOb (wherein M is at least one of Mn, Ni, Co and Al, x/y is greater than 0.51 and lower than 0.95, and b is not lower than 1 and not greater than 2). The method comprises the following steps: 1, weighing raw materials comprising a lithium sauce and at least one of a manganese source, a cobalt source, a nickel source and an aluminum source according to the molar ratio in xLi2O.yMOb; 2, adding a liquid into the raw materials, and grinding to form a slurry, wherein the median particle size D50 of particles of the slurry is less than 0.05mum; 3, drying the slurry in a spray manner; and 4, roasting the material obtained after drying. The method has the advantages of simple process and easy industrialized production; the primary particles of the obtained powder are small, and the secondary particles are spherical in shape; and the lithium-rich anode material prepared through adopting the method has a large discharge specific capacity, and the specific energy of the lithium ion battery prepared through using the lithium-rich anode material is high.
Description
Technical field
The present invention relates to field of lithium ion battery anode, specifically a kind of preparation method of lithium-rich anode material.
Background technology
After nineteen ninety, Sony successfully have developed new type lithium ion battery, lithium ion battery obtains and develops rapidly.It possess operating voltage high, lightweight, have extended cycle life, allow that working range is wide, memory-less effect, the advantage such as pollution-free, thus instead of the conventional batteries such as ickel-cadmium cell, Ni-MH battery and lead-acid battery, be widely used in the consumer electronic product that notebook computer, mobile phone, digital telephone etc. are small-sized.Along with increasing substantially of lithium ion battery specific energy, lithium ion battery becomes the oversize vehicles such as bus, electric automobile, hybrid electric vehicle gradually, the power resources of the LEV (Light Electric Vehicle) such as electric bicycle, Small-scale Flat battery vehicle and electric tool.But as the electrokinetic cell of oversize vehicle, lithium ion battery also needs to have greatly improved and could meet application requirement better in specific energy, cycle life, fail safe etc.As one of the critical material of lithium ion battery, the overall performance of performance on battery of positive electrode has to cause and closes important impact, so the positive electrode finding novel high power capacity becomes current research emphasis.
At present, lithium-rich anode material is because having higher charge/discharge capacity and good cyclical stability and being subject to extensive concern.Lithium-rich anode material is by the Li of stratiform
2mnO
3and LiMO
2the solid solution that (M=Mn, Ni, Co) is formed by different proportion, its chemical formula can be write as xLi
2mnO
3(1-x) LiMO
2or xLi
2oyMO
b(x/y > 0.51).The method preparing lithium-rich anode material has a lot, as coprecipitation, sol-gal process, high temperature solid-state method, hydrothermal synthesis method etc., wherein coprecipitation is the most conventional, the material that these methods are prepared can obtain good performance, as A.Manthiram etc. adopts coprecipitation to prepare lithium-rich anode material Li [Li
0.2mn
0.54ni
0.13co
0.13] O
2, when surface does not have coated, first discharge specific capacity reaches 250mAh/g (J.Phys.Chem.C., 114 (2010) 9528-9533), but these methods preparation technology engineering is complicated, and cost is high, is not suitable for industrialization and produces on a large scale.Young-Sik Hong etc. adopt spontaneous combustion legal system for Li [Ni
0.20li
0.20mn
0.60] O
2with Li [Co
0.20li
0.27mn
0.53] O
2, wherein Li [Ni
0.20li
0.20mn
0.60] O
2after 30 circulations, its specific discharge capacity only drops to 213mAh/g (Solid State Ionics from 288mAh/g, 176 (2005) 1035-1042), but the method needs the process of medium temperature on the one hand in preparation process, on the other hand, course of reaction due to spontaneous combustion method is difficult to control, and there is potential safety hazard, therefore is not suitable for industry and prepares lithium-rich anode material.Wang Jianhua etc. adopt the liquid phase reactor of controlled condition to obtain intermediate product, and then each component is pressed atomic level dispersion and formed solid solution, heat-treats the lithium ion anode active material (CN101662025A) of acquisition afterwards.This preparation process more complicated, has requirement to the temperature of reaction solution and the pH value of solution, and material require prepared by this method is heat-treated under oxygen atmosphere, each of which increases industrial cost, limits its development.
Summary of the invention
What the object of this invention is to provide a kind of applicable suitability for industrialized production prepares lithium-enriched cathodic material of lithium ion battery xLi
2oyMO
bmethod, and the positive pole of the lithium ion battery providing a kind of lithium-rich anode material with prepared by the present invention to make and lithium ion battery.In order to realize this object, the present invention takes following technical scheme:
A kind of lithium-rich anode material xLi
2oyMO
b, wherein M is at least one in Mn, Ni, Co, Al, 0.51 < x/y < 0.95,1≤b≤2, preparation method, the method is at least containing following 4 steps:
1) with lithium source, and at least one is selected from manganese source, cobalt source, nickel source, aluminium source as raw material, according to xLi
2oyMO
bin mol ratio take corresponding raw material;
2) add liquid in the feed, grind, to form the median particle diameter D of particle
50be less than the slurry of 0.05 μm, described grinding is at least divided into two steps, and first fine grinding makes the median particle diameter D of particle in slurry
50be less than 0.1 μm, then carry out the median particle diameter D that Ultrafine Grinding makes particle in slurry
50be less than 0.05 μm;
3) spray-dired mode is adopted to carry out drying in ground slurry;
4) dried material is carried out roasting, sintering temperature is 500 ~ 1100 DEG C, sintering temperature 5 ~ 60h.
It is in Mn, Ni, Co, Al at least two kinds that lithium-rich anode material prepared by the present invention is preferably M, 0.52 < x/y < 0.92,1.3≤b≤1.9.
In the present invention, lithium source is anhydrous lithium hydroxide, adds at least one in the lithium hydroxide of the crystallization water, lithium carbonate, preferred lithium carbonate.
Manganese source is at least one in manganese metal, manganese monoxide, manganese dioxide, manganese carbonate, preferable alloy manganese or manganese carbonate.
Nickel source is at least one in metallic nickel, nickel protoxide, nickel sesquioxide, nickel hydroxide, nickelous carbonate, preferable alloy nickel or nickel protoxide.
Cobalt source is at least one in metallic cobalt, cobalt protoxide, cobaltosic oxide, cobalt hydroxide, cobalt carbonate, preferable alloy cobalt or cobaltosic oxide.
Aluminium source is at least one in metallic aluminium, alundum (Al2O3), aluminium hydroxide.
When to select in following manganese source, cobalt source, nickel source, aluminium source two or three at the same time, following compound can be selected; When selecting manganese source, nickel source, manganese source, nickel source are at least one in manganese-nickel, manganous hydroxide nickel, hydroxyl oxidize manganese nickel, manganese oxalate nickel, manganese carbonate nickel, manganese oxide nickel simultaneously; When selecting manganese source, nickel source, cobalt source, manganese source, nickel source, cobalt source are at least one in manganese nickel cobalt alloy, hydroxide manganese nickel cobalt, hydroxyl oxidize manganese nickel cobalt, oxalic acid manganese nickel cobalt, carbonic acid manganese nickel cobalt, oxidation manganese nickel cobalt simultaneously; When selecting manganese source, cobalt source, manganese source, cobalt source are at least one in manganese cobalt alloy, manganous hydroxide cobalt, hydroxyl oxidize manganese cobalt, manganese oxalate cobalt, manganese carbonate manganese oxide cobalt simultaneously; When selecting nickel source, cobalt source, nickel source, cobalt source are at least one in nickel cobalt (alloy), nickel hydroxide cobalt, hydroxy cobalt nickel oxide, nickel oxalate cobalt, nickelous carbonate cobalt, cobalt nickel oxide simultaneously.
The raw material taken according to chemical formula joins in liquid, and wherein liquid adopts at least one in water, the aqueous solution of ethanol, the PVA aqueous solution, aqueous sucrose solution, at least one in preferred deionized water, distilled water; Or the preferably sucrose aqueous solution, at least one in the PVA aqueous solution.
Grind after mixing, grinding is at least divided into two steps, and first fine grinding makes the median particle diameter D of particle in slurry
50be less than 0.1 μm, then carry out the median particle diameter D that Ultrafine Grinding makes particle in slurry
50be less than 0.05 μm; Be preferably point three step grindings, first roughly grind the median particle diameter D that (first step grinding) makes primary particle in slurry
50be less than 1 μm, then fine grinding (second step grinding) makes the median particle diameter D of primary particle in slurry
50be less than 0.1 μm, finally carry out the median particle diameter D that Ultrafine Grinding (the 3rd step grinding) makes primary particle in slurry
50be less than 0.05 μm.Grain diameter is less, and the transmission range of lithium ion in positive electrode is shorter.Each step grinding adopts different milling apparatus.
The slurry formed after grinding is carried out spraying dry, utilizes atomizer that the slurry after grinding is separated into tiny droplet, dryly rapidly in thermal medium can form powder.The median particle diameter D of the primary particle of the powder of gained after spraying dry
50be less than 1 micron, be even less than 0.1 micron, be less than 0.05 micron.Primary particle is reunited and is formed the spherical second particle of 3-20 micron.By the powder high-temperature roasting that drying obtains, the temperature 500-1100 DEG C of roasting, the temperature of preferred roasting is 800-1000 DEG C, more preferably 800-950 DEG C; The time of roasting is 5 ~ 60h, and the time of preferred roasting is 12 ~ 48h; The particle primary particle size D of the lithium-rich anode material obtained after cooling
50be less than 1 micron, (primary particle refers to that inside does not have the dense material of hole to the spherical second particle of primary particle reunion formation 5 ~ 20 microns, and it can be monocrystalline, amorphous, also can be the not much higher crystalline substance of inner grain boundary density, i.e. particle farmland; Second particle is the aggregation of primary particle, is that individual particle is formed with weak binding power).
Adopt method of the present invention can prepare one in following lithium-rich anode material:
0.525Li
2O·0.96Mn
0.4Ni
0.3Co
0.3O
1.55、0.585Li
2O·0.83Mn
0.69Ni
0.29Co
0.02O
1.7、
0.6Li
2O·0.8Mn
0.675Ni
0.1625Co
0.1625O
1.75、0.6Li
2O·0.8Mn
0.7Ni
0.2Co
0.1O
1.75、
0.6Li
2O·0.8Mn
0.7375Ni
0.2375Co
0.025O
1.75、0.525Li
2O·0.95Mn
0.55Ni
0.45O
1.55、
0.545Li
2O·0.91Mn
0.6Ni
0.4O
1.6、0.55Li
2O·0.9Mn
0.61Ni
0.39O
1.61、0.555Li
2O·0.89Mn
0.63Ni
0.37O
1.62、
0.585Li
2O·0.83Mn
0.7Ni
0.3O
1.7、0.6Li
2O·0.8Mn
0.5Ni
0.5O
1.75、0.6Li
2O·0.8Mn
0.75Ni
0.25O
1.75、
0.625Li
2O·0.75Mn
0.83Ni
0.17O
1.83、0.585Li
2O·0.83Mn
0.6Co
0.4O
1.7、0.6Li
2O·0.8Mn
0.5Co
0.5O
1.75、
0.615Li
2O·0.77Mn
0.6Co
0.4O
1.8、0.63Li
2O·0.74Mn
0.7Co
0.3O
1.85、
0.6Li
2O·0.8Mn
0.7375Ni
0.2375Al
0.025O
1.75、0.585Li
2O·0.83Mn
0.69Ni
0.29Al
0.02O
1.7、
0.565Li
2O·0.87Mn
0.63Ni
0.33Al
0.04O
1.65、0.565Li
2O·0.87Mn
0.63Ni
0.33Al
0.04O
1.65、
0.565Li
2O·0.87Mn
0.3Ni
0.36Co
0.31Al
0.03O
1.65、0.585Li
2O·0.83Mn
0.4Ni
0.3Co
0.27Al
0.03O
1.7、
0.6Li
2O·0.8Mn
0.5Ni
0.25Co
0.225Al
0.025O
1.7、0.63Li
2O·0.74Mn
0.7Ni
0.15Co
0.14Al
0.014O
1.78、
0.645Li
2O·0.711Mn
0.8Ni
0.1Co
0.09Al
0.01O
1.85。
Mix with conductive agent, binding agent with the lithium-rich anode material prepared by the inventive method, dissolve in organic solvent, form anode sizing agent, be coated on supporter, make the positive pole of lithium ion battery.
Adopt this positive pole, and the negative pole selecting the lithium-rich anode material electricity prepared with the present invention compatible is as the negative pole of lithium ion battery, adds barrier film, electrolyte, composition lithium ion battery.
Advantage of the present invention is:
Compared with prior art, the method preparing lithium-rich anode material of the present invention is, with grinding, raw material grinding mill is become colloidal, in conjunction with the dry powder of spray drying process, do not adopt acid or alkali to prepare presoma (and the wet chemistry methods such as coprecipitation often adopt acid or alkali) on the one hand, there is not the pollution problem that acid or alkali bring, process environmental protection, energy-conservation, cost is low; Can obtain primary particle fine second particle by spray drying process is on the other hand spherical presoma, and by forming the spherical lithium-rich anode material of porous after high-temperature roasting, this material is easy to the deintercalation of lithium ion, thus improves the chemical property of material.Meanwhile, because the mixing of grinding technics Raw of the present invention is very even, makes in heat treatment process, decrease middle low-temperature bake process, reduce technique, thus reduce costs, be easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum that the present invention adopts colloid high-temperature synthesis synthetic example 1 [1 in Fig. 1)] and embodiment 2 [2 in Fig. 1)] positive electrode.
Fig. 2 is the field emission scanning electron microscope picture of the embodiment 2 that the present invention adopts colloid high-temperature synthesis to synthesize, wherein a and b is the SEM picture of the material after corase grind, fine grinding and Ultrafine Grinding, spraying dry and high-temperature roasting, the multiplication factor of a is the multiplication factor of 2k, b is 10k.
Fig. 3 is the present invention's embodiment 1 of adopting colloid high-temperature synthesis to synthesize and embodiment 2, at 0.1C, and the first charge-discharge curve comparison figure of material under 4.8 ~ 2.0V.
Fig. 4 is the present invention's embodiment 1 of adopting colloid high-temperature synthesis to synthesize and embodiment 2, at 4.8 ~ 2.0V, and the high rate performance comparison diagram of material.
Fig. 5 is the field emission scanning electron microscope picture of comparative example 2 of the present invention, comparative example 3 and comparative example 4, and wherein a and b is the corresponding comparative example 3, e of comparative example 2, c and d and the corresponding comparative example 4 of f, and wherein the multiplication factor of a, c, e is 2k, b, the multiplication factor of d, f is 10k.
Fig. 6 is the positive electrode that the embodiment of the present invention 2 and comparative example 1 and comparative example 2, comparative example 3, comparative example 4 are synthesized, 0.1C, the first charge-discharge curve comparison figure of material under 4.8 ~ 2.0V.
Fig. 7 is the positive electrode that the embodiment of the present invention 2 and comparative example 1, comparative example 2, comparative example 3, comparative example 4 are synthesized, 4.8 ~ 2.0V, the high rate performance comparison diagram of material.
Fig. 8 is the material of the 2-in-1 one-tenth of the embodiment of the present invention is positive electrode, and the lithium ion battery of assembling is at 0.2C, and under 4.25 ~ 3.0V, the energy density of material is with voltage change curve figure.
Embodiment
Be further described technical scheme of the present invention by embodiment below, will contribute to doing further understanding to preparation method of the present invention, protection scope of the present invention is not limited to the examples, and protection scope of the present invention is decided by claims.
Embodiment 1:
Weigh 103.97g lithium carbonate, 145.56g manganese carbonate, 17.97g metallic cobalt and 22.77g nickel protoxide, mixing, adds 800ml deionized water, joins in atomizer mill after fine grinding, after tested, and D
50be 0.09 micron, then take out, join Ultrafine Grinding machine and carry out Ultrafine Grinding, the D after Ultrafine Grinding
50it is 0.045 micron.Carry out spraying dry, the D of the primary particle after spraying dry
50be 0.046 micron, the spherical second particle 3-15 micron of formation.The powder obtained after point spraying dry is through 850 DEG C of calcination 48h, and with stove cooling, the powder of acquisition grinds, and crosses 300 mesh sieves.By analysis, prepared lithium-rich anode material consist of 0.6Li
2o0.8Mn
0.675ni
0.1625co
0.1625o
1.75.Through sintering after primary particle particle diameter at 0.8 ~ 1 micron, the particle diameter D of the second particle of formation
50it is 16.8 microns.
Embodiment 2:
Weigh 103.97g lithium carbonate, 145.56g manganese carbonate, 17.97g metallic cobalt and 22.77g nickel protoxide, join in corase grind tank, add 350ml deionized water, mixed, be placed on kibbling mill and roughly grind 24h.After tested, the D of primary particle
50it is 0.8 micron.Add 1000ml deionized water again and carry out fine grinding, through testing graininess, the D of primary particle
50it is 0.07 micron.Add 400ml deionized water again and carry out Ultrafine Grinding, through testing graininess, the D of primary particle
50it is 0.02 micron.Carry out spraying dry, the D of the primary particle after spraying dry
50be 0.02 micron, the spherical second particle of formation 3 ~ 15 microns.The powder obtained after spraying dry is through 850 DEG C of calcination 48h, and with stove cooling, the powder of acquisition grinds, and crosses 300 mesh sieves.By analysis, prepared lithium-rich anode material consist of 0.6Li
2o0.8Mn
0.675ni
0.1625co
0.1625o
1.75.Carry out testing graininess, the primary particle 0.5 ~ 1 micron of material after sintering, the D of second particle
50it is 15.2 microns.
The preparation condition of the material of embodiment 3 ~ 26 is as shown in the table,
Comparison example 1:
Weigh 103.97g lithium carbonate, 145.56g manganese carbonate, 17.97g metallic cobalt and 22.77g nickel protoxide, join in corase grind tank, add 350ml deionized water, mixed, be placed on bar type ball mill and roughly grind 24h.After tested, D
50be 2.1 microns, spraying dry, the primary particle after spraying dry is 0.4-1 micron, the spherical second particle D of formation
50it is 16 microns.The powder obtained after spraying dry is through 850 DEG C of calcination 48h, and with stove cooling, the powder of acquisition grinds, and crosses 300 mesh sieves.By analysis, prepared rich lithium solid solution consist of 0.6Li
2o0.8Mn
0.675ni
0.1625co
0.1625o
1.75.Through sintering after primary particle particle diameter at 0.8-1 micron, the particle diameter D of the second particle of formation
50it is 16.8 microns.
Comparison example 2:
Weigh 103.97g lithium carbonate, 145.56g manganese carbonate, 17.97g metallic cobalt and 22.77g nickel protoxide, be dry mixed 50h.Powder after being dry mixed is sintered 48h at 850 DEG C, cooling, grinding, by analysis, obtain 0.6Li
2o0.8Mn
0.675ni
0.1625co
0.1625o
1.75lithium-rich anode material.
Comparison example 3:
Weigh 32.33g nickel acetate, 32.38g cobalt acetate, 132.35g manganese acetate, join 2M KOH, formed precipitation, washing, drying precipitated, obtain manganese-cobalt-nickel precursor powder, add 66.33g lithium carbonate again, be dry mixed 12h, the powder after being dry mixed is sintered 48h at 850 DEG C, cooling, grinding, by analysis, obtains 0.6Li
2o0.8Mn
0.675ni
0.1625co
0.1625o
1.75lithium-rich anode material.
Comparison example 4:
Take 103.97g lithium carbonate, 145.56g manganese carbonate, 17.97g metallic cobalt and 22.77g nickel protoxide, add 1450ml deionized water, grind, after being mixed by raw material, put 100 DEG C of oven dry in an oven.Powder after drying is raised to 850 DEG C according to 4 DEG C/min heating rate, calcination 48h, and with stove cooling, the powder of acquisition grinds, and crosses 300 mesh sieves.By analysis, 0.6Li is obtained
2o0.8Mn
0.675ni
0.1625co
0.1625o
1.75lithium-rich anode material.
Fig. 1 is embodiment 1 and the XRD collection of illustrative plates (the XRD collection of illustrative plates of material prepared by other specific embodiment is similar, omits) of the material of 2 preparations, as can be seen from the figure, within the scope of 800 ~ 950 DEG C, obtains stratiform α-NaFeO
2layer structure, there is at 20 ~ 25 DEG C the superlattice structure that solid-solution material possesses in 2 θ.
Fig. 2 is the scanning electron microscopic picture of material prepared by embodiment 2, as can be seen from scanning electron microscopic picture, embodiment 2 is after high-temperature roasting, the particle diameter of the primary particle of material 0.5 ~ 1 μm, the diameter of spherical second particle is at 5 ~ 20 μm, and defining porous network structure, such structure is conducive to the embedding of lithium ion and deviates from.
Fig. 5 is the scanning electron microscopic picture of the material of comparative example 2, comparative example 3 and comparative example 4 preparation, as can be seen from scanning electron microscopic picture, after being dry mixed by raw material, in conjunction with compact between particle, does not form porous network structure.After the presoma adopting coprecipitation to prepare and lithium carbonate are dry mixed, the granular size obtained is relatively more even, but does not form spherical reticulated particle.Adopt ball milling, although do not have the material particle after spraying dry smaller, but do not form spherical reticulated particle.
Prepared by positive pole
Adopt the material of embodiment 1 and 2, comparative example 1 ~ 4 preparation as active material, weigh according to the proportioning of 8: 1: 1 with conductive agent (SP), binding agent (PVDF), first active material and conductive agent are dry mixed 4h, PVDF is dissolved in N-N dimethyl formamide, then the conductive agent of the active material mixed is added wherein, stir, form anode sizing agent, anode sizing agent is coated on aluminium foil, dries in drying box.
Prepared by testing of materials half-cell
The electrode cutting of having dried is become 1 × 1cm, then roll-in, dry at vacuum drying chamber, as the positive pole of battery, the negative pole of battery adopts lithium metal, the LiPF of the composition of electrolyte mainly 1M
6and DMC/EC/DEC (1: 1: 1), positive pole, negative pole and electrolyte are placed in container and form test battery.
The electrochemical property test of material
By the test battery of composition, be 20mA/g (0.1C) in current density, charging/discharging voltage scope 4.8 ~ 2V, the charge-discharge property of test battery.The high rate performance of test battery under 0.1C, 0.2C, 0.5C, 1C, 2C, 3C multiplying power.
The preparation of lithium ion battery
The material adopting embodiment 2 to prepare makes positive pole as active material, and native graphite makes negative pole as active material, selects the PP/PE/PP of three layers as barrier film, the LiPF of the composition of electrolyte mainly 1M
6and DMC/EC/DEC (1: 1: 1), make Soft Roll laminated lithium ion battery.
Battery performance test
By the lithium ion battery made, at 0.2C, voltage is the energy density of test battery under 4.25V ~ 3V.
Utilize positive electrode prepared by embodiment 1 and embodiment 2, the first charge-discharge comparison diagram of the battery of assembling as shown in Figure 3.As can be seen from Figure 3, the initial charge specific capacity of embodiment 2 is 406.7mAh/g, and specific discharge capacity is 285.6mAh/g, coulombic efficiency is 70.2%, and the initial charge specific capacity of embodiment 1 is 372.1mAh/g, specific discharge capacity is 260.6mAh/g, and coulombic efficiency is 70.0%.
Fig. 4 is the high rate performance comparison diagram of the lithium ion battery of positive electrode assembling prepared by embodiment 1 and 2, positive electrode prepared by embodiment 1, assembling lithium ion battery, battery is 260.6mAh/g at the specific discharge capacity of 0.1C, the specific discharge capacity of the specific discharge capacity of 0.2C to be the specific discharge capacity of 241.7mAh/g, 0.5C be 235.6mAh/g, 1C is 225.7mAh/g, the specific discharge capacity of 2C is the specific discharge capacity of 218.7mAh/g, 3C is 210.2mAh/g.Positive electrode prepared by embodiment 2, assembling lithium ion battery, battery is 285.6mAh/g at the specific discharge capacity of 0.1C, the specific discharge capacity of 0.2C is 255.7mAh/g, the specific discharge capacity of 0.5C is 249.3mAh/g, the specific discharge capacity of the specific discharge capacity of 1C to be the specific discharge capacity of 240.5mAh/g, 2C be 233.6mAh/g, 3C is 225.7mAh/g.Data show, and positive electrode prepared by embodiment 2 is no matter under high magnification or under low range, and performance is all better than embodiment 1, the embedding of the lithium ion in the charge and discharge process of particle size influences material is described and deviates from.
Fig. 6 is embodiment 2 and comparative example 1, comparative example 2, comparative example 3, the first charge-discharge comparison diagram of the battery of positive electrode assembling prepared by comparative example 4, as can be seen from Figure 6, the initial charge specific capacity of embodiment 2 is 406.7mAh/g, specific discharge capacity is 285.6mAh/g, coulombic efficiency is 70.2%, and the initial charge specific capacity of comparative example 1 is 370.3mAh/g, specific discharge capacity is 251.4mAh/g, coulombic efficiency is 67.9%, the initial charge specific capacity of comparative example 2 is 285.8mAh/g, specific discharge capacity is 192.7mAh/g, coulombic efficiency is 67.4%, the initial charge specific capacity of comparative example 3 is 328.0mAh/g, specific discharge capacity is 219.3mAh/g, coulombic efficiency is 66.9%, the initial charge specific capacity of comparative example 4 is 345.4mAh/g, specific discharge capacity is 236.2mAh/g, coulombic efficiency is 68.4%.
The high rate performance comparison diagram of the lithium ion battery of positive electrode assembling prepared by Fig. 7 embodiment 2 and comparative example 1, comparative example 2, comparative example 3, comparative example 4, the high rate performance of embodiment 2 is above-mentioned to be mentioned, positive electrode prepared by comparative example 1, assembling lithium ion battery, battery is 251.4mAh/g at the specific discharge capacity of 0.1C, the specific discharge capacity of 0.2C is 231.8mAh/g, the specific discharge capacity of 0.5C is 218.6mAh/g, the specific discharge capacity of 1C is 208.4mAh/g, the specific discharge capacity of 2C is the specific discharge capacity of 196.4mAh/g, 3C is 188.5mAh/g.Positive electrode prepared by comparative example 2, assembling lithium ion battery, battery is 192.7mAh/g at the specific discharge capacity of 0.1C, the specific discharge capacity of 0.2C is 182.5mAh/g, the specific discharge capacity of 0.5C is 176.7mAh/g, the specific discharge capacity of the specific discharge capacity of 1C to be the specific discharge capacity of 172.9mAh/g, 2C be 167.9mAh/g, 3C is 162.9mAh/g.Positive electrode prepared by comparative example 3, assembling lithium ion battery, battery is 219.3mAh/g at the specific discharge capacity of 0.1C, the specific discharge capacity of 0.2C is 205.1mAh/g, the specific discharge capacity of 0.5C is 200.5mAh/g, the specific discharge capacity of the specific discharge capacity of 1C to be the specific discharge capacity of 194.6mAh/g, 2C be 190.7mAh/g, 3C is 186.6mAh/g.Positive electrode prepared by comparative example 4, assembling lithium ion battery, battery is 236.2mAh/g at the specific discharge capacity of 0.1C, the specific discharge capacity of 0.2C is 218.4mAh/g, the specific discharge capacity of 0.5C is 214.6mAh/g, the specific discharge capacity of the specific discharge capacity of 1C to be the specific discharge capacity of 210.2mAh/g, 2C be 205.7mAh/g, 3C is 202.4mAh/g.Data show, positive electrode prepared by embodiment 2 at the specific discharge capacity of 3C higher than comparative example 1,2,3 and 4, in conjunction with above-mentioned data, method provided by the invention not only provides cost savings in technique, and the performance of material also reaches the requirement of electrokinetic cell, this method can be applied in industrial production.
As shown in Figure 8.The active material utilizing specific embodiment 2 to prepare is as the positive electrode of battery, and the energy density with reference to the lithium ion battery of above-mentioned method assembling is 254.4Wh/kg.
Positive electrode prepared by embodiment 3 ~ 26, assembling lithium ion battery, be 4.8 ~ 2.0V in voltage range, the discharge performance tables of data under different multiplying is as shown in the table.
Claims (32)
1. a preparation method for lithium-rich anode material, this lithium-rich anode material is xLi
2oyMO
b, wherein M is at least one in Mn, Ni, Co, Al, 0.51 < x/y < 0.95, and 1≤b≤2, is characterized in that, at least containing following 4 steps:
1) with lithium source, and at least one is selected from manganese source, cobalt source, nickel source, aluminium source as raw material, by xLi
2oyMO
bin mol ratio take corresponding raw material;
2) add liquid in the feed, grind, to form the median particle diameter D of particle
50be less than the slurry of 0.05 μm, described grinding is at least divided into two steps, and first fine grinding makes the median particle diameter D of particle in slurry
50be less than 0.1 μm, then carry out the median particle diameter D that Ultrafine Grinding makes particle in slurry
50be less than 0.05 μm;
3) spray-dired mode is adopted to carry out drying in ground slurry;
4) dried material is carried out roasting, sintering temperature is 500 ~ 1100 DEG C, roasting time 5 ~ 60h.
2. preparation method according to claim 1, is characterized in that, described step 2) in grinding be divided into three steps, first corase grind makes the median particle diameter D of primary particle in slurry
50be less than 1 μm, then fine grinding makes the median particle diameter D of primary particle in slurry
50be less than 0.1 μm, finally carry out the median particle diameter D that Ultrafine Grinding makes primary particle in slurry
50be less than 0.05 μm.
3. preparation method according to claim 1 and 2, is characterized in that, consisting of of described lithium-rich anode material: xLi
2oyMO
b, wherein M is in Mn, Ni, Co, Al at least two kinds, 0.52 < x/y < 0.92,1.3≤b≤1.9.
4. preparation method according to claim 1 and 2, is characterized in that, described lithium source is anhydrous lithium hydroxide, containing at least one in crystallization water lithium hydroxide, lithium carbonate.
5. the preparation method of lithium-rich anode material according to claim 4, is characterized in that, described lithium source is lithium carbonate.
6. preparation method according to claim 1 and 2, is characterized in that, described manganese source is at least one in manganese metal, manganese monoxide, manganese dioxide, manganese carbonate.
7. preparation method according to claim 6, is characterized in that, described manganese source is manganese metal.
8. preparation method according to claim 6, is characterized in that, described manganese source is manganese carbonate.
9. preparation method according to claim 1 and 2, is characterized in that, described nickel source is at least one in metallic nickel, nickel protoxide, nickel sesquioxide, nickel hydroxide, nickelous carbonate.
10. preparation method according to claim 9, is characterized in that, described nickel source is metallic nickel.
11. preparation methods according to claim 9, is characterized in that, described nickel source is nickel protoxide.
12. preparation methods according to claim 1 and 2, is characterized in that, described cobalt source is at least one in metallic cobalt, cobaltosic oxide, cobalt sesquioxide, cobalt protoxide, cobalt hydroxide, cobalt carbonate.
13. preparation methods according to claim 12, is characterized in that, described cobalt source is metallic cobalt.
The preparation method of 14. lithium-rich anode materials according to claim 12, is characterized in that, described cobalt source is cobaltosic oxide.
15. preparation methods according to claim 1 and 2, is characterized in that, described aluminium source is at least one in metallic aluminium, alundum (Al2O3), aluminium hydroxide.
16. preparation methods according to claim 1 and 2, is characterized in that, described manganese source, nickel source, cobalt source are at least one in manganese nickel cobalt alloy, hydroxide manganese nickel cobalt, hydroxyl oxidize manganese nickel cobalt, oxalic acid manganese nickel cobalt, carbonic acid manganese nickel cobalt, oxidation manganese nickel cobalt.
17. preparation methods according to claim 1 and 2, is characterized in that, described manganese source, nickel source are at least one in manganese-nickel, manganous hydroxide nickel, hydroxyl oxidize manganese nickel, manganese oxalate nickel, manganese carbonate nickel, manganese oxide nickel.
18. preparation methods according to claim 1 and 2, is characterized in that, described manganese source, cobalt source are at least one in manganese cobalt alloy, manganous hydroxide cobalt, hydroxyl oxidize manganese cobalt, manganese oxalate cobalt, manganese carbonate cobalt, manganese oxide cobalt.
19. preparation methods according to claim 1 and 2, is characterized in that, described nickel source, cobalt source are at least one in nickel cobalt (alloy), nickel hydroxide cobalt, hydroxy cobalt nickel oxide, nickel oxalate cobalt, nickelous carbonate cobalt, cobalt nickel oxide.
20. preparation methods according to claim 1 and 2, is characterized in that, described liquid is at least one in water, the aqueous solution of ethanol, the PVA aqueous solution, aqueous sucrose solution.
21. preparation methods according to claim 1 and 2, is characterized in that, described liquid is at least one in deionized water, distilled water.
22. preparation methods according to claim 20, is characterized in that, described liquid is at least one in the PVA aqueous solution, aqueous sucrose solution.
23. preparation methods according to claim 1 and 2, is characterized in that, described spraying dry is utilize atomizer that the slurry after grinding is separated into tiny droplet, and rapid drying forms the process of powder in thermal medium.
24. preparation methods according to claim 23, is characterized in that, after spraying dry, gained powder is the spherical second particle that particle diameter is less than the primary particle reunion formation 3-20 micron of 1 μm.
25., according to preparation method described in claim 23, is characterized in that, after spraying dry, gained powder is the spherical second particle that particle diameter is less than the primary particle reunion formation 3-20 micron of 0.1 μm.
26. preparation methods according to claim 23, is characterized in that, after spraying dry, gained powder is the primary particle that particle diameter is less than 0.05 μm, the spherical second particle forming 3-20 μm of reuniting.
27. preparation methods according to claim 1 and 2, is characterized in that, the temperature of roasting is 800 ~ 1000 DEG C.
28. preparation methods according to claim 27, is characterized in that, the temperature of roasting is 800 ~ 950 DEG C.
29. preparation methods according to claim 1 and 2, is characterized in that, the median particle diameter D of the primary particle of the powder after roasting
50particle diameter is less than 1 μm, and the second particle of powder is 5 ~ 20 μm.
30. preparation methods according to claim 1 and 2, is characterized in that, described lithium-rich anode material is the one in following composition: 0.525Li
2o0.96Mn
0.4ni
0.3co
0.3o
1.55, 0.585Li
2o0.83Mn
0.69ni
0.29co
0.02o
1.7, 0.6Li
2o0.8Mn
0.675ni
0.1625co
0.1625o
1.75, 0.6Li
2o0.8Mn
0.7ni
0.2co
0.1o
1.75, 0.6Li
2o0.8Mn
0.7375ni
0.2375co
0.025o
1.75, 0.525Li
2o0.95Mn
0.55ni
0.45o
1.55, 0.545Li
2o0.91Mn
0.6ni
0.4o
1.6, 0.55Li
2o0.9Mn
0.61ni
0.39o
1.61, 0.555Li
2o0.89Mn
0.63ni
0.37o
1.62, 0.585Li
2o0.83Mn
0.7ni
0.3o
1.7, 0.6Li
2o0.8Mn
0.5ni
0.5o
1.75, 0.6Li
2o0.8Mn
0.75ni
0.25o
1.75, 0.625Li
2o0.75Mn
0.83ni
0.17o
1.83, 0.585Li
2o0.83Mn
0.6co
0.4o
1.7, 0.6Li
2o0.8Mn
0.5co
0.5o
1.75, 0.615Li
2o0.77Mn
0.6co
0.4o
1.8, 0.63Li
2o0.74Mn
0.7co
0.3o
1.85, 0.6Li
2o0.8Mn
0.7375ni
0.2375al
0.025o
1.75, 0.585Li
2o0.83Mn
0.69ni
0.29al
0.02o
1.7, 0.565Li
2o0.87Mn
0.63ni
0.33al
0.04o
1.65, 0.565Li
2o0.87Mn
0.63ni
0.33al
0.04o
1.65, 0.565Li
2o0.87Mn
0.3ni
0.36co
0.31al
0.03o
1.65, 0.585Li
2o0.83Mn
0.4ni
0.3co
0.27al
0.03o
1.7, 0.6Li
2o0.8Mn
0.5ni
0.25co
0.225al
0.025o
1.7, 0.63Li
2o0.74Mn
0.7ni
0.15co
0.14al
0.014o
1.78, 0.645Li
2o0.711Mn
0.8ni
0.1co
0.09al
0.01o
1.85.
The positive pole of 31. 1 kinds of lithium ion batteries, it is characterized in that, lithium-rich anode material preparation method as described in claim 1-30 any one prepared mixes with conductive carbon and bonding agent, and the mixture obtained is coated in the positive pole supporting and conducting base is formed described lithium ion battery.
32. 1 kinds of lithium ion batteries, is characterized in that, anode compatible with electricity for positive pole according to claim 31, barrier film, electrolyte are placed in container and form described lithium ion battery.
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| CN104347868B (en) * | 2013-08-02 | 2017-07-14 | 国联汽车动力电池研究院有限责任公司 | A kind of lithium ion battery positive electrode of lithium-rich containing magnesium and preparation method thereof |
| CN103996845A (en) * | 2014-05-26 | 2014-08-20 | 东莞市迈科科技有限公司 | Composite lithium-rich positive electrode material and preparation method thereof |
| JP6193493B2 (en) * | 2014-06-20 | 2017-09-06 | 株式会社フジミインコーポレーテッド | Powder material used for powder additive manufacturing and powder additive manufacturing method using the same |
| CN105789558A (en) * | 2014-12-24 | 2016-07-20 | 北京有色金属研究总院 | High-rate capability lithium-rich manganese-based cathode material for lithium-ion battery and preparation method of high-rate capability lithium-rich manganese-based cathode material |
| CN105304893A (en) * | 2015-09-25 | 2016-02-03 | 湖北宇电能源科技股份有限公司 | Preparation method of lithium ion battery anode active material lithium nickel manganese oxide |
| CN105244501B (en) * | 2015-09-25 | 2018-02-02 | 湖北工程学院 | A kind of active material of lithium ion battery electrode presoma manganese carbonate nickel |
| CN105355907B (en) * | 2015-12-10 | 2018-03-30 | 哈尔滨工业大学 | Positive electrode and preparation method prepared by lithium metal oxide persursor material and the material with " annual ring " formula structure |
| CN105938899B (en) * | 2016-06-01 | 2019-05-10 | 中南大学 | A kind of preparation method and application of fast-ionic conductor coating modification anode material for lithium-ion batteries |
| CN107528056B (en) * | 2017-08-28 | 2020-06-02 | 四川富骅新能源科技有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN107768639A (en) * | 2017-10-19 | 2018-03-06 | 深圳市比克动力电池有限公司 | Anode material of lithium battery and preparation method thereof, the lithium battery using the positive electrode |
| CN108172776A (en) * | 2017-11-25 | 2018-06-15 | 合肥国轩高科动力能源有限公司 | Li2MnO3And LiCrO2Composite positive pole and synthetic method |
| CN109987650B (en) * | 2019-04-26 | 2021-11-09 | 清华大学深圳研究生院 | Nickel cobalt lithium manganate positive electrode material, preparation method and application thereof |
| CN110311128A (en) * | 2019-07-10 | 2019-10-08 | 深圳市本征方程石墨烯技术股份有限公司 | A kind of lithium cobaltate cathode material and preparation method thereof of graphene doping |
| CN113772743B (en) * | 2021-09-30 | 2023-06-23 | 青岛天尧新材料有限公司 | Preparation method of manganese cobalt composite oxide powder |
| CN114873650A (en) * | 2022-05-24 | 2022-08-09 | 中国科学院宁波材料技术与工程研究所 | Positive electrode material precursor, positive electrode material and preparation method thereof, and lithium ion battery |
| CN115140784B (en) * | 2022-07-28 | 2023-10-03 | 南昌大学 | Lithium-rich ternary positive electrode material and preparation method and application thereof |
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