CN103094550A - Preparation method of lithium-rich anode material - Google Patents
Preparation method of lithium-rich anode material Download PDFInfo
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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 the anode material for lithium-ion batteries field, specifically a kind of preparation method of lithium-rich anode material.
Background technology
After nineteen ninety, Sony successfully developed new type lithium ion battery, lithium ion battery had obtained developing 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, thereby replaced the conventional batteries such as ickel-cadmium cell, Ni-MH battery and lead-acid battery, be widely used in the small-sized consumer electronic products such as notebook computer, mobile phone, digital telephone.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 at aspects such as specific energy, cycle life, fail safes and could satisfy better application requirements.As one of critical material of lithium ion battery, the performance of positive electrode has to cause on the overall performance of battery closes important impact, becomes present research emphasis so seek the positive electrode of novel high power capacity.
At present, lithium-rich anode material because of have higher charge/discharge capacity and preferably cyclical stability be subject to extensive concern.Lithium-rich anode material is the Li by stratiform
2MnO
3And LiMO
2(M=Mn, Ni, Co) presses the solid solution that different proportion forms, and its chemical formula can be write as xLi
2MnO
3(1-x) LiMO
2Or xLi
2OyMO
b(x/y＞0.51).The method for 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 commonly used, the material that these methods are prepared can be obtained good performance, has prepared lithium-rich anode material Li[Li as employing coprecipitations such as A.Manthiram
0.2Mn
0.54Ni
0.13Co
0.13] O
2, in the situation that the surface does not coat, 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 the production of large-scale industrialization.Young-Sik Hong etc. adopt the spontaneous combustion legal system for Li[Ni
0.20Li
0.20Mn
0.60] O
2And Li[Co
0.20Li
0.27Mn
0.53] O
2, Li[Ni wherein
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 processing of medium temperature on the one hand in preparation process, on the other hand, control because the course of reaction of spontaneous combustion method is very difficult, have potential safety hazard, therefore be not suitable for industry preparation lithium-rich anode material.The liquid phase reactor of the employing controlled conditions such as Wang Jianhua obtains intermediate product, and then each component is pressed the atomic level dispersion and formed solid solution, heat-treats afterwards the lithium ion anode active material (CN101662025A) of acquisition.This preparation process more complicated has requirement to the temperature of reaction solution and the pH value of solution, and the material require of this method preparation heat-treats under oxygen atmosphere, and these have all increased industrial cost, have limited its development.
Summary of the invention
The preparation lithium-enriched cathodic material of lithium ion battery xLi that the purpose of this invention is to provide a kind of suitable suitability for industrialized production
2OyMO
bMethod, and provide a kind of positive pole and lithium ion battery of the lithium ion battery made from the prepared lithium-rich anode material of the present invention.In order to realize this purpose, the present invention takes following technical scheme:
A kind of lithium-rich anode material xLi
2OyMO
b, wherein M is at least a in Mn, Ni, Co, Al, 0.51＜x/y＜0.95,1≤b≤2, the preparation method, the method contains following 4 steps at least:
1) with the lithium source, and be selected from manganese source, cobalt source, nickel source, aluminium source at least a as raw material, according to xLi
2OyMO
bIn a mole proportioning take corresponding raw material;
2) add liquid in raw material, grind, to form the median particle diameter D of particle
50Less than the slurry of 0.05 μ m, described grinding was divided into for two steps at least, and first fine grinding makes the median particle diameter D of particle in slurry
50Less than 0.1 μ m, then carry out the median particle diameter D that Ultrafine Grinding makes particle in slurry
50Less than 0.05 μ m;
3) adopt spray-dired mode to carry out drying in ground slurry;
4) dried material is carried out roasting, sintering temperature is 500～1100 ℃, sintering temperature 5～60h.
The prepared lithium-rich anode material of the present invention preferably M is in Mn, Ni, Co, Al at least two kinds, 0.52＜x/y＜0.92,1.3≤b≤1.9.
In the present invention, the lithium source is anhydrous lithium hydroxide, it is at least a to add in the lithium hydroxide of the crystallization water, lithium carbonate, preferred lithium carbonate.
The manganese source is at least a in manganese metal, manganese monoxide, manganese dioxide, manganese carbonate, preferable alloy manganese or manganese carbonate.
The nickel source is at least a in metallic nickel, nickel protoxide, nickel sesquioxide, nickel hydroxide, nickelous carbonate, preferable alloy nickel or nickel protoxide.
The cobalt source is at least a in metallic cobalt, cobalt protoxide, cobaltosic oxide, cobalt hydroxide, cobalt carbonate, preferable alloy cobalt or cobaltosic oxide.
The aluminium source is at least a in metallic aluminium, alundum (Al2O3), aluminium hydroxide.
Select at the same time in following manganese source, cobalt source, nickel source, aluminium source can to select following compound in two or three situation; When selecting simultaneously manganese source, nickel source, manganese source, nickel source is at least a in manganese-nickel, manganous hydroxide nickel, hydroxyl oxidize manganese nickel, manganese oxalate nickel, manganese carbonate nickel, manganese oxide nickel; When selecting simultaneously manganese source, nickel source, cobalt source, manganese source, nickel source, cobalt source is at least a 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; When selecting simultaneously manganese source, cobalt source, manganese source, cobalt source is at least a in manganese cobalt alloy, manganous hydroxide cobalt, hydroxyl oxidize manganese cobalt, manganese oxalate cobalt, manganese carbonate manganese oxide cobalt; When selecting simultaneously nickel source, cobalt source, nickel source, cobalt source is at least a in nickel cobalt (alloy), nickel hydroxide cobalt, hydroxy cobalt nickel oxide, nickel oxalate cobalt, nickelous carbonate cobalt, cobalt nickel oxide.
The raw material that takes according to chemical formula joins in liquid, and is wherein at least a in the aqueous solution of liquid employing water, ethanol, the PVA aqueous solution, aqueous sucrose solution, at least a in preferred deionized water, distilled water; Or at least a in the preferably sucrose aqueous solution, the PVA aqueous solution.
Grind after mixing, grinding was divided into for two steps at least, and first fine grinding makes the median particle diameter D of particle in slurry
50Less than 0.1 μ m, then carry out the median particle diameter D that Ultrafine Grinding makes particle in slurry
50Less than 0.05 μ m; Be preferably minute three a steps grinding, first corase grind (first step grinding) makes the median particle diameter D of primary particle in slurry
50Less than 1 μ m, then fine grinding (second step grinding) makes the median particle diameter D of primary particle in slurry
50Less than 0.1 μ m, carry out at last the median particle diameter D that Ultrafine Grinding (the 3rd step ground) makes primary particle in slurry
50Less than 0.05 μ m.Grain diameter is less, and the transmission range of lithium ion in positive electrode is shorter.Each step grinds and adopts different milling apparatus.
The slurry that forms after grinding is carried out spray drying, utilize the slurry after atomizer will grind to be separated into tiny droplet, can rapid drying form powder in thermal medium.The median particle diameter D of the primary particle of the powder of gained after spray drying
50Less than 1 micron, even less than 0.1 micron, less than 0.05 micron.Primary particle is reunited and is formed the spherical second particle of 3-20 micron.With the powder high-temperature roasting that drying obtains, the temperature 500-1100 of roasting ℃, the temperature of preferred roasting is 800-1000 ℃, more preferably 800-950 ℃; 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 of cooling rear acquisition
50Less than 1 micron, primary particle is reunited, and (primary particle refers to that inside does not have the dense material of hole to the spherical second particle that forms 5～20 microns, and it can be monocrystalline, amorphous, can be also the not much higher crystalline substance of inner crystal boundary density, i.e. particle farmland; Second particle is the aggregation of primary particle, is that individual particle consists of with weak adhesion).
Adopt method of the present invention can prepare a kind of 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。
The lithium-rich anode material prepared with the inventive method mixes with conductive agent, binding agent, is dissolved in organic solvent, forms anode sizing agent, is coated on supporter, makes the positive pole of lithium ion battery.
Adopt this positive pole, and the compatible negative pole of the lithium-rich anode material electricity of selection and the present invention preparation adds barrier film, electrolyte as the negative pole of lithium ion battery, form lithium ion battery.
Advantage of the present invention is:
Compared with prior art, the method for preparing lithium-rich anode material of the present invention is with grinding, raw material grinding mill to be 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, the pollution problem that does not exist acid or alkali to bring, process environmental protection, energy-conservation, cost is low; Can make primary particle fine second particle by spray drying process on the other hand is spherical presoma, and by forming the spherical lithium-rich anode material of porous after high-temperature roasting, this material is easy to the embedding of taking off of lithium ion, thereby has improved the chemical property of material.Simultaneously, because the mixing of grinding technics Raw of the present invention is very even, make the low-temperature bake process in the middle of having reduced in heat treatment process, reduce technique, thereby reduce costs, be easy to suitability for industrialized production.
Description of drawings
Fig. 1 is that the present invention adopts 1 in colloid high-temperature synthesis synthetic example 1[Fig. 1)] and embodiment 2[Fig. 1 in 2)] X ray diffracting spectrum of positive electrode.
Fig. 2 is the field emission scanning electron microscope picture that the present invention adopts the synthetic embodiment 2 of colloid high-temperature synthesis, wherein a and b are the SEM picture of the material after corase grind, fine grinding and Ultrafine Grinding, spray drying and high-temperature roasting, the multiplication factor of a is 2k, and the multiplication factor of b is 10k.
Fig. 3 is that the present invention adopts colloid high-temperature synthesis synthetic embodiment 1 and embodiment 2, at 0.1C, and the first charge-discharge curve comparison figure of material under 4.8～2.0V.
Fig. 4 is that the present invention adopts colloid high-temperature synthesis synthetic embodiment 1 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 Examples 2 of the present invention, Comparative Examples 3 and Comparative Examples 4, and wherein a and b are Comparative Examples 2, the corresponding Comparative Examples 3 of c and d, and the corresponding Comparative Examples 4 of e and f, wherein the multiplication factor of a, c, e is 2k, the multiplication factor of b, d, f is 10k.
Fig. 6 is the embodiment of the present invention 2 and Comparative Examples 1 and Comparative Examples 2, Comparative Examples 3, the synthetic positive electrode of Comparative Examples 4,0.1C, 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 Examples 1, Comparative Examples 2, Comparative Examples 3, Comparative Examples 4 are synthesized, 4.8～2.0V, the high rate performance comparison diagram of material.
Fig. 8 is that the embodiment of the present invention 2 synthetic materials are 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 the change in voltage curve chart.
Embodiment
Below with embodiment, technical scheme of the present invention is further described, will help preparation method of the present invention is done further understanding, protection scope of the present invention is not subjected to the restriction of these embodiment, protection scope of the present invention is decided by claims.
Embodiment 1:
Weighing 103.97g lithium carbonate, 145.56g manganese carbonate, 17.97g metallic cobalt and 22.77g nickel protoxide mix, and add the 800ml deionized water, join in atomizer mill after fine grinding, after tested, D
50Be 0.09 micron, then take out, join the Ultrafine Grinding machine and carry out Ultrafine Grinding, the D after Ultrafine Grinding
50It is 0.045 micron.Carry out spray drying, the D of the primary particle after spray drying
50Be 0.046 micron, the spherical second particle 3-15 micron of formation.The powder that obtains after minute spray drying is through 850 ℃ of calcination 48h, and is cooling with stove, and the powder of acquisition grinds, and crosses 300 mesh sieves.By analysis, prepared lithium-rich anode material consists of 0.6Li
2O0.8Mn
0.675Ni
0.1625Co
0.1625O
1.75Primary particle particle diameter after sintering is at 0.8～1 micron, the particle diameter D of the second particle of formation
50It is 16.8 microns.
Embodiment 2:
Weighing 103.97g lithium carbonate, 145.56g manganese carbonate, 17.97g metallic cobalt and 22.77g nickel protoxide join in the corase grind tank, add the 350ml deionized water, with its mixing, are placed on and roughly grind 24h on kibbling mill.After tested, the D of primary particle
50It is 0.8 micron.Add again the 1000ml deionized water to carry out fine grinding, through testing graininess, the D of primary particle
50It is 0.07 micron.Add again the 400ml deionized water to carry out Ultrafine Grinding, through testing graininess, the D of primary particle
50It is 0.02 micron.Carry out spray drying, the D of the primary particle after spray drying
50Be 0.02 micron, 3～15 microns of the spherical second particles of formation.The powder that obtains after spray drying is through 850 ℃ of calcination 48h, and is cooling with stove, and the powder of acquisition grinds, and crosses 300 mesh sieves.By analysis, prepared lithium-rich anode material consists of 0.6Li
2O0.8Mn
0.675Ni
0.1625Co
0.1625O
1.75Carry out testing graininess, 0.5～1 micron of the primary particle of material after sintering, the D of second particle
50It is 15.2 microns.
The material preparation condition of embodiment 3～26 is as shown in the table,
Comparison example 1:
Weighing 103.97g lithium carbonate, 145.56g manganese carbonate, 17.97g metallic cobalt and 22.77g nickel protoxide join in the corase grind tank, add the 350ml deionized water, with its mixing, are placed on the bar type ball mill and roughly grind 24h.After tested, D
50Be 2.1 microns, spray drying, the primary particle after spray drying is the 0.4-1 micron, the spherical second particle D of formation
50It is 16 microns.The powder that obtains after spray drying is through 850 ℃ of calcination 48h, and is cooling with stove, and the powder of acquisition grinds, and crosses 300 mesh sieves.By analysis, prepared rich lithium solid solution consists of 0.6Li
2O0.8Mn
0.675Ni
0.1625Co
0.1625O
1.75Primary particle particle diameter after sintering is at the 0.8-1 micron, the particle diameter D of the second particle of formation
50It is 16.8 microns.
Comparison example 2:
Weighing 103.97g lithium carbonate, 145.56g manganese carbonate, 17.97g metallic cobalt and 22.77g nickel protoxide are dry mixed 50h.Powder after being dry mixed is at 850 ℃ of sintering 48h, cooling, grind, by analysis, obtain 0.6Li
2O0.8Mn
0.675Ni
0.1625Co
0.1625O
1.75Lithium-rich anode material.
Comparison example 3:
Weighing 32.33g nickel acetate, 32.38g cobalt acetate, 132.35g manganese acetate, join 2M KOH, form precipitation, washing, drying precipitated, obtain manganese-cobalt-nickel precursor powder, add again the 66.33g lithium carbonate, be dry mixed 12h, with the powder after being dry mixed at 850 ℃ of sintering 48h, cooling, grind, by analysis, obtain 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 the 1450ml deionized water, grind, after raw material is mixed, be placed on 100 ℃ of oven dry in baking oven.Powder after oven dry is raised to 850 ℃ according to 4 ℃/min heating rate, calcination 48h, cooling with stove, the powder of acquisition grinds, and crosses 300 mesh sieves.By analysis, obtain 0.6Li
2O0.8Mn
0.675Ni
0.1625Co
0.1625O
1.75Lithium-rich anode material.
Fig. 1 is the XRD collection of illustrative plates (the XRD collection of illustrative plates of the material of other specific embodiment preparation is similar, omits) of embodiment 1 and the material of 2 preparations, as can be seen from the figure, in 800～950 ℃ of scopes, has obtained stratiform α-NaFeO
2Layer structure, 2 θ the superlattice structure that solid-solution material possesses occurred at 20～25 ℃.
Fig. 2 is the ESEM picture of the material of embodiment 2 preparations, can find out from the ESEM picture, embodiment 2 is after high-temperature roasting, particle diameter 0.5～1 μ m of the primary particle of material, the diameter of spherical second particle is at 5～20 μ m, and having formed porous network structure, such structure is conducive to the embedding of lithium ion and deviates from.
Fig. 5 is the ESEM picture of the material of Comparative Examples 2, Comparative Examples 3 and Comparative Examples 4 preparations, can find out from the ESEM picture, after raw material is dry mixed, in conjunction with compact, does not form porous network structure between particle.After the presoma of employing coprecipitation preparation and lithium carbonate were dry mixed, the granular size that obtains was more even, but does not form spherical reticulated particle.Adopt ball milling, though do not have the material particle after spray drying smaller, spherical reticulated particle do not formed.
Anodal preparation
Adopt the material of embodiment 1 and 2, Comparative Examples 1～4 preparation as active material, with the proportioning weighing according to 8: 1: 1 of conductive agent (SP), binding agent (PVDF), first active material and conductive agent are dry mixed 4h, PVDF is dissolved in the N-N dimethyl formamide, then the conductive agent with the active material that mixes adds wherein, stirs, and forms anode sizing agent, anode sizing agent is coated on aluminium foil, dries in drying box.
Testing of materials prepares with half-cell
The electrode cutting that oven dry is good becomes 1 * 1cm, and then roll-in is dry at vacuum drying chamber, and as the positive pole of battery, the negative pole of battery adopts lithium metal, and the composition of electrolyte is mainly the LiPF of 1M
6And DMC/EC/DEC (1: 1: 1), positive pole, negative pole and electrolyte are placed in container form test battery.
The electrochemical property test of material
With the test battery that forms, 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
Adopt the material of embodiment 2 preparations to make positive pole as active material, native graphite is made negative pole as active material, selects the PP/PE/PP of three layers as barrier film, and the composition of electrolyte is mainly the LiPF of 1M
6And DMC/EC/DEC (1: 1: 1), make the Soft Roll laminated lithium ion battery.
Battery performance test
With the lithium ion battery of making, at 0.2C, voltage is the energy density of test battery under 4.25V～3V.
Utilize the positive electrode of embodiment 1 and embodiment 2 preparations, 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, enclosed pasture efficient is 70.2%, and the initial charge specific capacity of embodiment 1 is 372.1mAh/g, and specific discharge capacity is 260.6mAh/g, and enclosed pasture efficient is 70.0%.
Fig. 4 is the high rate performance comparison diagram of lithium ion battery of the positive electrodes assembling of embodiment 1 and 2 preparations, the positive electrode of embodiment 1 preparation, the assembling lithium ion battery, battery is 260.6mAh/g at the specific discharge capacity of 0.1C, 0.2C specific discharge capacity be 241.7mAh/g, the specific discharge capacity of 0.5C is 235.6mAh/g, the specific discharge capacity of 1C is 225.7mAh/g, the specific discharge capacity of 2C is 218.7mAh/g, and the specific discharge capacity of 3C is 210.2mAh/g.The positive electrode of embodiment 2 preparations, the assembling lithium ion battery, battery is 285.6mAh/g at the specific discharge capacity of 0.1C, 0.2C specific discharge capacity be 255.7mAh/g, 0.5C specific discharge capacity be 249.3mAh/g, the specific discharge capacity of 1C is 240.5mAh/g, and the specific discharge capacity of 2C is 233.6mAh/g, and the specific discharge capacity of 3C is 225.7mAh/g.Data show, no matter under high magnification or under low range, performance all is better than embodiment 1 to the positive electrode of embodiment 2 preparations, the embedding of the lithium ion in the particle size influences be described charge and discharge process of material and deviating from.
Fig. 6 is embodiment 2 and Comparative Examples 1, Comparative Examples 2, Comparative Examples 3, the first charge-discharge comparison diagram of the battery of the positive electrode assembling of Comparative Examples 4 preparations, 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, enclosed pasture efficient is 70.2%, and the initial charge specific capacity of Comparative Examples 1 is 370.3mAh/g, specific discharge capacity is 251.4mAh/g, enclosed pasture efficient is 67.9%, the initial charge specific capacity of Comparative Examples 2 is 285.8mAh/g, specific discharge capacity is 192.7mAh/g, enclosed pasture efficient is 67.4%, the initial charge specific capacity of Comparative Examples 3 is 328.0mAh/g, specific discharge capacity is 219.3mAh/g, enclosed pasture efficient is 66.9%, the initial charge specific capacity of Comparative Examples 4 is 345.4mAh/g, specific discharge capacity is 236.2mAh/g, enclosed pasture efficient is 68.4%.
The high rate performance comparison diagram of the lithium ion battery of the positive electrode assembling of Fig. 7 embodiment 2 and Comparative Examples 1, Comparative Examples 2, Comparative Examples 3, Comparative Examples 4 preparations, the high rate performance of embodiment 2 is above-mentioned to be mentioned, the positive electrode of Comparative Examples 1 preparation, the assembling lithium ion battery, battery is 251.4mAh/g at the specific discharge capacity of 0.1C, 0.2C specific discharge capacity be 231.8mAh/g, 0.5C specific discharge capacity be 218.6mAh/g, the specific discharge capacity of 1C is 208.4mAh/g, the specific discharge capacity of 2C is 196.4mAh/g, and the specific discharge capacity of 3C is 188.5mAh/g.The positive electrode of Comparative Examples 2 preparations, the assembling lithium ion battery, battery is 192.7mAh/g at the specific discharge capacity of 0.1C, 0.2C specific discharge capacity be 182.5mAh/g, 0.5C specific discharge capacity be 176.7mAh/g, the specific discharge capacity of 1C is 172.9mAh/g, and the specific discharge capacity of 2C is 167.9mAh/g, and the specific discharge capacity of 3C is 162.9mAh/g.The positive electrode of Comparative Examples 3 preparations, the assembling lithium ion battery, battery is 219.3mAh/g at the specific discharge capacity of 0.1C, 0.2C specific discharge capacity be 205.1mAh/g, 0.5C specific discharge capacity be 200.5mAh/g, the specific discharge capacity of 1C is 194.6mAh/g, and the specific discharge capacity of 2C is 190.7mAh/g, and the specific discharge capacity of 3C is 186.6mAh/g.The positive electrode of Comparative Examples 4 preparations, the assembling lithium ion battery, battery is 236.2mAh/g at the specific discharge capacity of 0.1C, 0.2C specific discharge capacity be 218.4mAh/g, 0.5C specific discharge capacity be 214.6mAh/g, the specific discharge capacity of 1C is 210.2mAh/g, and the specific discharge capacity of 2C is 205.7mAh/g, and the specific discharge capacity of 3C is 202.4mAh/g.Data show, the positive electrode of embodiment 2 preparation at the specific discharge capacity of 3C higher than Comparative Examples 1,2,3 and 4, in conjunction with above-mentioned data, method provided by the invention not only provides cost savings on technique, and the performance of material also reached the requirement of electrokinetic cell, and this method can be applied on industrial production.
As shown in Figure 8.Utilize the active material of specific embodiment 2 preparations as the positive electrode of battery, the energy density of the lithium ion battery of the method assembling that reference is above-mentioned is 254.4Wh/kg.
The positive electrode of embodiment 3～26 preparations, the assembling lithium ion battery is 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. lithium-rich anode material xLi
2OyMO
b, wherein M is at least a in Mn, Ni, Co, Al, 0.51＜x/y＜0.95,1≤b≤2, the preparation method, it is characterized in that, contain at least following 4 steps:
1) with the lithium source, and be selected from manganese source, cobalt source, nickel source, aluminium source at least aly as raw material, press xLi
2OyMO
bIn a mole proportioning take corresponding raw material;
2) add liquid in raw material, grind, to form the median particle diameter D of particle
50Less than the slurry of 0.05 μ m, described grinding was divided into for two steps at least, and first fine grinding makes the median particle diameter D of particle in slurry
50Less than 0.1 μ m, then carry out the median particle diameter D that Ultrafine Grinding makes particle in slurry
50Less than 0.05 μ m;
3) adopt spray-dired mode to carry out drying in ground slurry;
4) dried material is carried out roasting, sintering temperature is 500～1100 ℃, sintering temperature 5～60h.
2. the preparation method of lithium-rich anode material according to claim 1, is characterized in that, described step 2) in grinding be divided into for three steps, first corase grind makes the median particle diameter D of primary particle in slurry
50Less than 1 μ m, then fine grinding makes the median particle diameter D of primary particle in slurry
50Less than 0.1 μ m, carry out at last the median particle diameter D that Ultrafine Grinding makes primary particle in slurry
50Less than 0.05 μ m.
3. the preparation method of lithium-rich anode material according to claim 1 and 2, is characterized in that, the 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. the preparation method of lithium-rich anode material according to claim 1 and 2, is characterized in that, described lithium source is anhydrous lithium hydroxide, it is at least a to contain 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. the preparation method of lithium-rich anode material according to claim 1 and 2, is characterized in that, described manganese source is at least a in manganese metal, manganese monoxide, manganese dioxide, manganese carbonate.
7. the preparation method of lithium-rich anode material according to claim 6, is characterized in that, described manganese source is manganese metal.
8. the preparation method of lithium-rich anode material according to claim 6, is characterized in that, described manganese source is manganese carbonate.
9. the preparation method of lithium-rich anode material according to claim 1 and 2, is characterized in that, described nickel source is at least a in metallic nickel, nickel protoxide, nickel sesquioxide, nickel hydroxide, nickelous carbonate.
10. the preparation method of lithium-rich anode material according to claim 9, is characterized in that, described nickel source is metallic nickel.
11. the preparation method of lithium-rich anode material according to claim 9 is characterized in that, described nickel source is nickel protoxide.
12. the preparation method of lithium-rich anode material according to claim 1 and 2 is characterized in that, described cobalt source is at least a in metallic cobalt, cobaltosic oxide, cobalt sesquioxide, cobalt protoxide, cobalt hydroxide, cobalt carbonate.
13. the preparation method of lithium-rich anode material according to claim 12 is characterized in that, described cobalt source is metallic cobalt.
14. the preparation method of lithium-rich anode material according to claim 12 is characterized in that, described cobalt source is cobaltosic oxide.
15. the preparation method of lithium-rich anode material according to claim 1 and 2 is characterized in that, described aluminium source is at least a in metallic aluminium, alundum (Al2O3), aluminium hydroxide.
16. the preparation method of lithium-rich anode material according to claim 1 and 2, it is characterized in that, described manganese source, nickel source, cobalt source is at least a 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. the preparation method of lithium-rich anode material according to claim 1 and 2 is characterized in that, described manganese source, nickel source is at least a in manganese-nickel, manganous hydroxide nickel, hydroxyl oxidize manganese nickel, manganese oxalate nickel, manganese carbonate nickel, manganese oxide nickel.
18. the preparation method of lithium-rich anode material according to claim 1 and 2 is characterized in that, described manganese source, cobalt source is at least a in manganese cobalt alloy, manganous hydroxide cobalt, hydroxyl oxidize manganese cobalt, manganese oxalate cobalt, manganese carbonate cobalt, manganese oxide cobalt.
19. the preparation method of lithium-rich anode material according to claim 1 and 2 is characterized in that, described nickel source, cobalt source is at least a in nickel cobalt (alloy), nickel hydroxide cobalt, hydroxy cobalt nickel oxide, nickel oxalate cobalt, nickelous carbonate cobalt, cobalt nickel oxide.
20. the preparation method of lithium-rich anode material according to claim 1 and 2 is characterized in that, described liquid is at least a in the aqueous solution, the PVA aqueous solution, aqueous sucrose solution of water, ethanol.
21. the preparation method of lithium-rich anode material according to claim 1 and 2 is characterized in that, described liquid is at least a in deionized water, distilled water.
22. the preparation method of lithium-rich anode material according to claim 20 is characterized in that, described liquid is at least a in the PVA aqueous solution, aqueous sucrose solution.
23. the preparation method of lithium-rich anode material according to claim 1 and 2 is characterized in that, described spray drying is to utilize the slurry after atomizer will grind to be separated into tiny droplet, and in thermal medium the rapid dry process that forms powder.
24. the preparation method of lithium-rich anode material according to claim 23 is characterized in that, after spray drying, the gained powder is that particle diameter forms the spherical second particle of 3-20 micron less than the primary particle reunion of 1 μ m.
25. the preparation method of lithium-rich anode material according to claim 23 is characterized in that, after spray drying, the gained powder is that particle diameter forms the spherical second particle of 3-20 micron less than the primary particle reunion of 0.1 μ m.
26. the preparation method of lithium-rich anode material according to claim 23 is characterized in that, after spray drying the gained powder be particle diameter less than the primary particle of 0.05 μ m, reunite to form the spherical second particle of 3-20 μ m.
27. the preparation method of lithium-rich anode material according to claim 1 and 2 is characterized in that, the temperature of roasting is 800～1000 ℃.
28. the preparation method of lithium-rich anode material according to claim 27 is characterized in that, the temperature of roasting is 800～950 ℃.
29. the preparation method of lithium-rich anode material 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 μ m, and the second particle of powder is 5～20 μ m.
30. method according to claim 1 and 2 is characterized in that, described lithium-rich anode material is a kind of 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
31. the positive pole of a lithium ion battery, it is characterized in that, to mix with conductive carbon and bonding agent as the lithium-rich anode material of method preparation as described in claim 1-30 any one, and the mixture that obtains is coated in the positive pole that supports the described lithium ion battery of formation on conducting base.
32. a lithium ion battery is characterized in that, anode, barrier film, the electrolyte that the described positive pole of claim 31 is compatible with electricity is placed in container and forms described lithium ion battery.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219262A (en) * | 2011-05-10 | 2011-10-19 | 北京科技大学 | Improved method for preparing layered enriched lithium-manganese-nickel oxide by low-heat solid-phase reaction |
-
2011
- 2011-10-31 CN CN201110337732.6A patent/CN103094550B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219262A (en) * | 2011-05-10 | 2011-10-19 | 北京科技大学 | Improved method for preparing layered enriched lithium-manganese-nickel oxide by low-heat solid-phase reaction |
Non-Patent Citations (1)
| Title |
|---|
| 孙学磊: "球形磷酸铁锂正极材料制备中试研究", 《中国有色金属学报》 * |
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