CN102244236A - Method for preparing lithium-enriched cathodic material of lithium ion battery - Google Patents
Method for preparing lithium-enriched cathodic material of lithium ion battery Download PDFInfo
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Abstract
The invention provides a method for preparing a lithium-enriched cathodic material Li[LixMnyM(1-x-y)]O2(0 is less than x, y is less than 0.5, M is equal Mn0.5Ni0.5 or Mnx'Niy'Co(1-x'-y'), 0 is less than x', y' is less than 0.5), which comprises the following steps of: preparing a stable precursor by a hydrothermal auxiliary oxalate coprecipitation method, so that divalent manganese (II) can be prevented from being oxidized by air in solution, and obtaining solid solution of which metal elements such as Ni, Co, Mn and the like are distributed uniformly in an atomic level, so that the prepared lithium-enriched cathodic material has the high electrochemical activity; and wrapping a layer of graphene material with high conductivity on the surface of the lithium-enriched material uniformly to improve the magnification performance and circular stable performance of the lithium-enriched material obviously. In the method, the reaction process is not needed to be protected by inert gases, so the reaction is simplified and the cost is saved; the prepared lithium-enriched cathodic material is uniform in granules and high in electrochemical activity, and has the specific capacity of more than 250 mAh/g; the magnification performance and circular stable performance of the product is high; and the preparation is high in process repeatability, and the fluctuation of the physico-chemical performance of materials prepared by different batches is small.
Description
Technical field:
The invention belongs to chemical power source material preparation and anode material for lithium-ion batteries field, relate to a kind of method for preparing anode material for lithium-ion batteries.
Background technology
Advantages such as it is big that lithium ion battery has energy density, has extended cycle life, in light weight, pollution-free are the efficient portable chemical power supplys of a new generation.Aspects such as radio communication, digital camera, notebook computer and space technology have been widely used in now.Along with the further lifting of lithium ion battery energy density and power density, will progressively be applied to fields such as electric tool, electric bicycle, electric automobile (EV), hybrid vehicle (HEV) and extensive accumulate.
Positive electrode plays decisive role to the battery performance of lithium-ion-power cell, fail safe, cost etc., and its development has been subjected to extensive concern, and has urgency.
Present stage, main commercial anode material for lithium-ion batteries was mainly LiCoO
2, LiFePO
4, LiMn
2O
4, LiMn
xNi
yCo
(1-x-y)O
2(0＜x, y＜0.5) etc.LiCoO wherein
2Because Co
3+Have toxicity, and cobalt is scarce resource, material cost height, poor stability; LiMn
2O
4Capacity has only about 120mAh/g, and capacity is on the low side, and in cyclic process the Jahn-Teller distortion takes place easily, influences the stable circulation performance of material, and the high-temperature behavior of material is also not good enough; LiFePO
4Because its intrinsic electronics and ionic conductivity are poor, and be difficult to synthetic pure phase, and realization capacity and tap density are taken into account.The nearly stage, new system lithium ion battery Li-S battery is subjected to people and pays close attention to, wherein the reversible capacity of positive electrode S reaches more than the 800mAh/g, but be faced with the decay that the shuttle phenomenon causes its capacity that flies that its polysulfide dissolves in electrolyte, the cyclical stability of material is relatively poor, and the simple substance lithium forms the SEI film easily on the surface, dendrite, the problems such as deposition of polysulfide of dissolving influence the cyclicity, particularly fail safe of material.LiMn
xNi
yCo
(1-x-y)O
2(0＜x, y＜0.5) comprehensive LiCoO
2, LiMnO
2And LiNiO
2Advantage, obtain the concern of a lot of research groups.And the another kind that is all this type of stratified material is based on rock salt structure Li
2MnO
3Lithium-rich anode material Li[Li
xMn
yM
(1-x-y)] O
2(0＜x, y＜0.5, M=Mn
0.5Ni
0.5Or M=Mn
X 'Ni
Y ' Co
(1-x '-y ')0＜x ', y '＜0.5) begins in recent years extensively to be paid close attention to, the specific capacity of this type of material is up to 200mAh/g～300mAh/g (about theoretical capacity 300mAh/g), can satisfy the demand of following lithium-ion-power cell high-energy-density, also be hopeful most present stage, one of the most potential power lithium-ion battery positive electrode.
Canada Jeff Dahn research group is precipitation reagent with LiOH, synthetic precursor Ni
xMn
(1-x)(OH)
2, prepare the binary lithium-rich anode material Li[Ni of excellent performance first
xLi
1/3-2x/3Mn
2/3-x/3] O
2Korea S Hong and Park research group adopt the synthetic rich lithium material Li[Ni of simple combustion method with the colloidal sol precursor
xLi
1/3-2x/3Mn
2/3-x/3] O
2, discharge capacity reaches as high as 288mAh/g first when 20mA/g.Japan NEDO subsidizes a class Li of research and development
1+x(Fe
0.2Ni
0.2Mn
0.6)
1-xO
2Rich its specific discharge capacity of lithium material also can be greater than 250mAh/g.The Yang Han of Wuhan University west group adopts the synthetic preferable Li[Li of performance of polymer method for pyrolysis
0.12Ni
0.32Mn
0.56] O
2The Chen Gang of Jilin University, Wei Ying enter group lithium ion kinetics of diffusion in the rich lithium are studied.
Patent application " lithium-rich manganese-based anode material and preparation method thereof " (application number: 200910186311.0) disclose lithium-rich manganese-based anode material Li[Li
(1-2x)/3Ni
X-aM
yMn
(2-x)/3-b] O
2(M=Co, Al, Ti, Mg, Cu) and preparation method thereof; Patent application " a kind of method of modifying of high-rate lithium-rich material " (application number: 200910085461.2) disclose a kind of to lithium-rich anode material Li[Li
xNi
1/3-2x/Mn
2/3-x/3] O
2MnO carries out (1/5≤x≤1/3)
2Coat the method for improving the material high rate performance of handling; A kind of cobalt nickel oxide manganses lithium anode material of rich lithium type layer structure has been announced in patent application " lithium ion battery positive pole material cobalt nickel oxide manganses lithium " (application number 200610130302.6); Patent application " a kind of preparation method of composite anode material of high-capacity lithium ion battery " (application number: 200910303612.7,200910043712.0) disclose the method for utilizing ball milling to prepare lithium-rich anode material in conjunction with solid-phase sintering process; Patent application " a kind of anode material for lithium-ion batteries Li
1+x(Co
yMn
zNi
1-y-z)
1-xO
2And preparation method thereof " (application number: 200610150194.9) disclose a kind of soluble inorganic salt solution and solubility strong base solution prepared by co-precipitation presoma of utilizing, generated the method for lithium-rich anode material again with the lithium-containing compound sintering.
In the preparation technology of this class lithium-rich anode material, whether Ni, Co and Mn distribution evenly is the key factor that influences material structure and chemical property in the presoma.Current the most frequently used preparation method is a hydroxide coprecipitation step, promptly prepares Ni, Co, Mn hydroxide co-precipitation presoma earlier, and then adds lithium salts, makes after high-temperature process.This is that the dispersion of Ni, Co and Mn is very even because of in Ni, Co, the Mn precipitation of hydroxide, and the rich lithium material that makes at last has better crystalline form, and performance is also good than additive methods such as high temperature solid-state methods.Yet bivalent manganese in the hydroxide coprecipitation step preparation process (II) easily is oxidized to tetravalence manganese (IV), causes preparation technology's poor repeatability, easily produces dephasign, and the product fluctuation is big, thereby has had a strong impact on the performance of end product.Therefore, when hydroxide coprecipitation step prepares material, usually need to use argon shield, this makes that reaction is complicated, has increased the control difficulty, and the use of argon gas has simultaneously improved cost.
Given this, we do oxalate precipitation reagent first and are incorporated in rich lithium material synthetic, as the synthetic rich lithium material of precursor, make the embedding of material take off the reason capacity and cycle performance obviously improves with oxalic acid unit coprecipitate stable under the non-alkali condition of normal temperature.
In addition, though rich lithium material Li[Li
xMn
yM
(1-x-y)] O
2(0＜x, y＜0.5, M=Mn
0.5Ni
0.5Or M=Mn
X 'Ni
Y 'Co
(1-x '-y '), 0＜x ', y '＜0.5) and have high specific capacity, but studies show that both at home and abroad there is following problem in this class material: the electron conduction of material intrinsic and ionic conductivity be not good to cause high rate performance, heavy-current discharge performance poor; For the stability of material property, there is very big-difference in the report of different documents; The erosion that composition in the material is subjected to electrolyte causes cyclicity not good; The first charge-discharge efficiency of material is lower.
Therefore, at the problem of rich lithium material in high rate performance and stable circulation performance, the present invention utilizes graphene oxide to be reduced into the method for Graphene at rich lithium material surface in situ, plan is improved the multiplying power and the cycle performance of material by the Graphene that even coating-doping has high conductivity and high structural stability.For solving the crucial difficult point that this class material is applied to power battery anode material, should set about from preparation technology's innovation, solution is proposed.
Summary of the invention:
Purpose of the present invention is exactly at lithium-rich anode material Li[Li
xMn
yM
(1-x-y)] O
2(0＜x, y＜0.5, M=Mn
0.5Ni
0.5Or M=Mn
X 'Ni
Y 'Co
(1-x '-y '), 0＜x ', y '＜0.5) and the problem that exists, a kind of new preparation method has been proposed, this method is with low cost, and is simple and easy to do.At first, the presoma of oxalate coprecipitation method preparation is more stable, can avoid bivalent manganese (II) oxidation by air in solution, obtain metallic elements such as Ni, Co and Mn at last and reach the equally distributed oxalates solid solution of atom level, make the lithium-rich anode material of preparation have very high electro-chemical activity.Secondly, utilize the method for in-situ reducing graphene oxide,, can obviously improve the high rate performance and the stable circulation performance of rich lithium material at the grapheme material that rich lithium material coated with uniform one deck has high conductivity.
The present invention is achieved through the following technical solutions:
Nickel salt, cobalt salt and manganese salt are dissolved in the deionized water with certain stoichiometric proportion, stir, obtain even mixed solution; Press the total mole number of metal ion in nickel salt, cobalt salt and the manganese salt, take by weighing the oxalic acid that contains identical molal quantity oxalate denominationby or the oxalates of solubility, be dissolved in and obtain second kind of aqueous solution in the deionized water; Above-mentioned two kinds of aqueous solution equal-volumes are splashed in the reactor of continuous stirring uniformly, after fully mixing reactor is sealed, place 100～200 ℃ of baking ovens, continue reaction 3～24 hours, cooling, obtain the oxalate coprecipitation thing that nickel cobalt manganese is evenly distributed, in precipitation process, the pH value of solution is controlled between 4～8.5; Coprecipitate after filtration, washing, dry back obtain precursor with even mixing of the lithium salts of certain stoichiometric proportion, in air atmosphere that precursor is first 400～600 ℃ of following constant temperature pre-burnings 3～8 hours, be pressed into sheet then, obtained rich lithium oxide Li[Li in 6～18 hours at 700 ℃～950 ℃ sintering temperatures again
xMn
yM
(1-x-y)] O
2(0＜x, y＜0.5, M=Mn
0.5Ni
0.5Or M=Mn
X 'Ni
Y 'Co
(1-x '-y '), 0＜x ', y '≤0.5); Rich lithium oxide is ground to form the powder of particle diameter at 0.1～1 μ m, the utilization sonicated, powder is dispersed in the single or multiple lift graphite oxide aqueous solution that concentration is 0.1～10mg/ml, the vitamin C aqueous solution that adds certain stoichiometric proportion then, stir, make graphene oxide be reduced into Graphene, after filtration, washing and dry, obtain the lithium ion battery lithium-rich anode material at rich lithium oxide powder surface in situ.
The oxalates of above-mentioned solubility is one or several in sodium oxalate, potassium oxalate, potassium tetroxalate dihydrate and the ammonium oxalate.
Above-mentioned nickel salt is one or more in nickel acetate, nickel nitrate, nickelous sulfate and the nickel chloride; Above-mentioned cobalt salt is one or more in cobalt acetate, cobalt nitrate, cobaltous sulfate and the cobalt chloride, and above-mentioned manganese salt is one or more in manganese acetate, manganese nitrate, manganese sulfate and the manganese chloride.
Above-mentioned lithium-containing compound is one or several in lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate and the lithium chloride.
Above-mentioned graphite oxide aqueous solution makes by the acid system stripping technology, and with low cost, purity is higher.
The invention has the advantages that:
First, owing to replace hydroxide as precipitation reagent with oxalates, reaction generates oxalate precipitation, because manganese oxalate (II) is more stable in water than manganous hydroxide (II), therefore avoided the oxidation of bivalent manganese (II), thereby avoided the generation of dephasign, not blanketing with inert gas of course of reaction when using coprecipitation to prepare precursor, simplified reaction, provided cost savings; Product electro-chemical activity height, specific capacity be greater than 250mAh/g, good cycle; And this method good process repeatability, the fluctuation of product physical and chemical performance is little.
The second, adopt graphene oxide in-situ reducing technology, can realize the even coating of Graphene to rich lithium material, can obviously improve the multiplying power and the stable circulation performance of rich lithium material.
Description of drawings
Fig. 1 adopts the lithium-rich anode material Li[Ni of the inventive method preparation
0.2Li
0.2Mn
0.6] O
2The XRD diffracting spectrum.
Fig. 2 adopts the lithium-rich anode material Li[Ni of the inventive method preparation
0.2Li
0.2Mn
0.6] O
2Stereoscan photograph.
Fig. 3 adopts the lithium-rich anode material Li[Ni of the inventive method preparation
0.2Li
0.2Mn
0.6] O
2The cycle performance curve.
Embodiment
Embodiment 1: preparation lithium-rich anode material Li[Ni
0.2Li
0.2Mn
0.6] O
2, i.e. Li[Li
xMn
yM
(1-x-y)] O
2(x=0.2, y=0.2, M=Mn
0.5Ni
0.5).
At room temperature, mixture of a certain amount of nickel nitrate, manganese nitrate (wherein the ratio of nickel ion and manganese ion is 1: 1) and ammonium oxalate are dissolved in the water respectively.Ammonium oxalate solution and mixture solution are evenly splashed in the reactor, fully mix, reaction with the reactor sealing, places 180 ℃ of baking ovens then, and 12 as a child took out, and natural cooling generates the oxalate coprecipitation that nickel manganese is evenly distributed.With oxalate precipitation for several times, filter oven dry with deionized water wash.A certain amount of lithium carbonate of the precipitation powder of oven dry is ground evenly,, be pressed into sheet after the cooling, calcine down at 850 ℃ and obtained well-crystallized, the rich lithium oxide Li[Ni that chemical property is good in 12 hours 450 ℃ of following constant temperature pre-burnings 6 hours
0.2Li
0.2Mn
0.6] O
2With rich lithium oxide grind into powder, the utilization sonicated, powder is dispersed in the single or multiple lift graphite oxide aqueous solution that concentration is 3mg/ml, the vitamin C aqueous solution that adds certain stoichiometric proportion then, stir, make graphene oxide be reduced into Graphene, after filtration, washing and dry, obtain the lithium ion battery lithium-rich anode material at rich lithium oxide powder surface in situ.
Figure of description Fig. 1 is this lithium-rich anode material Li[Ni just
0.2Li
0.2Mn
0.6] O
2The XRD figure spectrum of sample.Can observe some more weak diffraction maximums in the XRD figure spectrum between 2 θ=20 °～25 °, these diffraction maximums are because Li
+And Mn
4+Cause at the transition metal layer orderly arrangement in more among a small circle formation superlattice.Li in the C2/m space group
2MnO
3Structure cell in, Li
+And Mn
4+In transition metal layer, arrange in order, therefore in its standard x RD spectrogram, also have 20 °～25 ° characteristic diffraction peak.And at Li[Ni
0.2Li
0.2Mn
0.6] O
2XRD spectra in faint diffraction maximum between having occurred 20 °～25 °, show at internal memory more among a small circle at small Li
2MnO
3The phase farmland shows Li[Ni
0.2Li
0.2Mn
0.6] O
2Be with Li
2MnO
3-LiNi
0.5Mn
0.5O
2The form of solid solution exists.Except these the faint diffraction maximums between 20 °～25 °, other stronger diffraction peak intensities are all very high, these diffraction maximums and LiNi
0.5Mn
0.5O
2Characteristic diffraction peak is similar, can simply that these are stronger diffraction maximum belongs to have the symmetric O of R-3m
3-LiCoO
2The characteristic peak of the layer structure of type.The XRD figure spectrum goes up (006)/(102) in addition and the two pairs of clear ground cleaves in peak in (008)/(110) separately come, and shows synthetic Li[Ni
0.2Li
0.2Mn
0.6] O
2Show good layer structure feature.
Figure of description Fig. 2 is this lithium-rich anode material Li[Ni
0.2Li
0.2Mn
0.6] O
2The sem photograph of sample, material granule is spherical as can be seen from Figure 2, and the average diameter of particle is less than 500nm, and having among a small circle reunites takes place, and the floccule of particle surface is a grapheme material.
Figure of description Fig. 3 is this lithium-rich anode material Li[Ni
0.2Li
0.2Mn
0.6] O
2The discharge capacity cycle graph of sample.First discharge specific capacity is at 228mAh/g, and discharge capacity rises to 260mAh/g after the circulation of 10 weeks, is being recycled to for the 30th week, and reversible specific discharge capacity still remains on about 260mAh/g.
Embodiment 2: preparation lithium-rich anode material Li[Li
0.2Mn
0.54Co
0.13Ni
0.13] O
2, i.e. Li[Li
xMn
yM
(1-x-y)] O
2(x=0.2, y=0.4, M=Mn
0.5Ni
0.5Co
0.5).
At room temperature, mixture of a certain amount of nickelous sulfate, cobaltous sulfate and manganese sulfate (wherein the ratio of nickel ion, cobalt ions and manganese ion is 1: 1: 1) and sodium oxalate are dissolved in the water respectively.Sodium oxalate solution and mixture solution are evenly splashed in the reactor, fully mix, reaction with the reactor sealing, places 200 ℃ of baking ovens then, and 12 as a child took out, and natural cooling generates the oxalate coprecipitation that nickel cobalt manganese is evenly distributed.With oxalate precipitation for several times, filter oven dry with deionized water wash.A certain amount of lithium carbonate of the precipitation powder of oven dry is ground evenly,, be pressed into sheet after the cooling, calcine down at 800 ℃ and obtained well-crystallized, the rich lithium oxide Li[Li that chemical property is good in 15 hours 500 ℃ of following constant temperature pre-burnings 5 hours
0.2Mn
0.54Co
0.13Ni
0.13] O
2With rich lithium oxide grind into powder, the utilization sonicated, powder is dispersed in the single or multiple lift graphite oxide aqueous solution that concentration is 5mg/ml, the vitamin C aqueous solution that adds certain stoichiometric proportion then, stir, make graphene oxide be reduced into Graphene, after filtration, washing and dry, obtain the lithium ion battery lithium-rich anode material at rich lithium oxide powder surface in situ.
XRD test shows Li[Li
0.2Mn
0.54Co
0.13Ni
0.13] O
2Be with Li
2MnO
3-LiNi
0.5Mn
0.5O
2The form of solid solution exists.The surface sweeping electron microscopic observation finds that the average diameter of particle is less than 400nm.The constant current charge-discharge experiment shows that the reversible doff lithium capacity of material reaches 289mAh/g.
Embodiment 3: preparation lithium-rich anode material Li[Li
0.2Mn
0.4Co
0.2Ni
0.2] O
2, i.e. Li[Li
xMn
yM
(1-x-y)] O
2(x=0.2, y=0.2, M=Mn
0.5Ni
0.5Co
0.5).
At room temperature, mixture of a certain amount of nickelous sulfate, cobaltous sulfate and manganese sulfate (wherein the ratio of nickel ion, cobalt ions and manganese ion is 1: 1: 1) and sodium oxalate are dissolved in the water respectively.Sodium oxalate solution and mixture solution are evenly splashed in the reactor, fully mix, reaction with the reactor sealing, places 150 ℃ of baking ovens then, and 18 as a child took out, and natural cooling generates the oxalate coprecipitation that nickel cobalt manganese is evenly distributed.With oxalate precipitation for several times, filter oven dry with deionized water wash.A certain amount of lithium carbonate of the precipitation powder of oven dry is ground evenly,, be pressed into sheet after the cooling, calcine down at 900 ℃ and obtained well-crystallized, the rich lithium oxide Li[Li that chemical property is good in 10 hours 550 ℃ of following constant temperature pre-burnings 4.5 hours
0.2Mn
0.4Co
0.2Ni
0.2] O
2With rich lithium oxide grind into powder, the utilization sonicated, powder is dispersed in the multilayer graphite oxide aqueous solution that concentration is 4mg/ml, the vitamin C aqueous solution that adds certain stoichiometric proportion then, stir, make graphene oxide be reduced into Graphene, after filtration, washing and dry, obtain the lithium ion battery lithium-rich anode material at rich lithium oxide powder surface in situ.
XRD test shows Li[Li
0.2Mn
0.4Co
0.2Ni
0.2] O
2Be with Li
2MnO
3-LiNi
0.5Mn
0.5O
2The form of solid solution exists.The surface sweeping electron microscopic observation finds that the average diameter of particle is less than 500nm.The constant current charge-discharge experiment shows that the reversible doff lithium capacity of material is greater than 280mAh/g.
Claims (4)
1. the preparation method of a lithium ion battery lithium-rich anode material is characterized in that: nickel salt, cobalt salt and manganese salt are dissolved in the deionized water with certain stoichiometric proportion, stir, obtain even mixed solution; Press the total mole number of metal ion in nickel salt, cobalt salt and the manganese salt, take by weighing the oxalic acid that contains identical molal quantity oxalate denominationby or the oxalates of solubility, be dissolved in and obtain second kind of aqueous solution in the deionized water; Above-mentioned two refreshing aqueous solution equal-volumes are splashed in the reactor of continuous stirring uniformly, after fully mixing reactor is sealed, place 100～200 ℃ of baking ovens, continue reaction 3～24 hours, cooling, obtain the oxalate coprecipitation thing that nickel cobalt manganese is evenly distributed, in precipitation process, the pH value of solution is controlled between 4～8.5; Coprecipitate after filtration, washing, dry back obtain precursor with even mixing of the lithium salts of certain stoichiometric proportion, in air atmosphere that precursor is first 400～600 ℃ of following constant temperature pre-burnings 3～8 hours, be pressed into sheet then, obtained rich lithium oxide Li[Li in 6～18 hours at 700 ℃～950 ℃ sintering temperatures again
xMn
yM
(1-x-y)] O
2(0＜x, y＜0.5, M=Mn
0.5Ni
0.5Or M=Mn
X 'Ni
Y 'Co
(1-x '-y '), 0＜x ', y '≤0.5); Rich lithium oxide is ground to form the powder of particle diameter at 0.1～1 μ m, the utilization sonicated, powder is dispersed in the graphite oxide aqueous solution that concentration is 0.1～10mg/ml, the vitamin C aqueous solution that adds certain stoichiometric proportion then, stir, make graphene oxide be reduced into Graphene, after filtration, washing and dry, obtain the lithium ion battery lithium-rich anode material at rich lithium oxide powder surface in situ.
2. the preparation method of a kind of lithium ion battery lithium-rich anode material according to claim 1, the oxalates of described solubility is one or more in sodium oxalate, potassium oxalate, potassium tetroxalate dihydrate and the ammonium oxalate.
3. the preparation method of a kind of lithium ion battery lithium-rich anode material according to claim 1, described nickel salt is one or more in nickel acetate, nickel nitrate, nickelous sulfate and the nickel chloride; Described cobalt salt is one or more in cobalt acetate, cobalt nitrate, cobaltous sulfate and the cobalt chloride, and described manganese salt is one or more in manganese acetate, manganese nitrate, manganese sulfate and the manganese chloride.
4. the preparation method of a kind of lithium ion battery lithium-rich anode material according to claim 1, described lithium salts is one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate and the lithium chloride.
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