CN102655232A - Preparation method of lithium manganese base-enriched ternary composite anode material - Google Patents

Preparation method of lithium manganese base-enriched ternary composite anode material Download PDF

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CN102655232A
CN102655232A CN2012101495924A CN201210149592A CN102655232A CN 102655232 A CN102655232 A CN 102655232A CN 2012101495924 A CN2012101495924 A CN 2012101495924A CN 201210149592 A CN201210149592 A CN 201210149592A CN 102655232 A CN102655232 A CN 102655232A
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lithium
ternary composite
manganese
positive pole
preparation
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吴锋
陈实
仲云霞
白莹
吴川
包丽颖
吴伯荣
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Beijing Institute of Technology BIT
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Abstract

The invention relates to a preparation method of lithium manganese base-enriched ternary composite anode material, belonging to the field of green energy resource material. The method comprises the following steps of: stirring to make the mixture dissolve so as to obtain mixed solution; putting precipitator in the water to dissolve in a stirring way, so that precipitator solution can be obtained; mixing the mixed solution with the precipitator solution to obtain reaction liquid, adjusting the pH value of the reaction liquid into 7.0-12.0, stirring for reaction, aging, filtering to obtain precipitate, and washing the precipitate by detergent; cooling the washed precipitate into the temperature which is less than or equal to -10 DEG C, and freezing for the time which is more than or equal to 1h, and drying under the vacuum degree which is less than or equal to 10.0Pa, so that a precursor can be obtained; and mixing the precursor with the lithium salt to carry out thermal treatment, so that the lithium manganese base-enriched ternary composite anode material can be obtained. The material prepared by the method is small in granularity, even in particle size distribution, and high in activity, so that the first irreversible capacity can be reduced, and the cycle performance of the lithium ion secondary battery taking the material as the anode material can be improved.

Description

A kind of preparation method of lithium-rich manganese-based ternary composite positive pole
Technical field
The present invention relates to a kind of preparation method of lithium-rich manganese-based ternary composite positive pole, specifically, the present invention relates to a kind of preparation method who is used as the lithium-rich manganese-based trielement composite material of lithium ion secondary battery anode material, belong to the green energy resource field of materials.
Background technology
Lithium rechargeable battery is as the rechargeable type high-energy battery of a new generation; Have the operating voltage height, numerous advantages such as energy density is big, security performance good, have extended cycle life and self discharge is low; After nineteen ninety Japan SONY energy technology company makes lithium rechargeable battery success commercialization; Be widely used in many portable electronic instrument equipment such as mobile phone, notebook computer and instrument and meter at present; Simultaneously, also has good application prospects in fields such as electric automobile, electric tool and energy storage peak load stations.
The positive electrode of lithium rechargeable battery is one of principal element that influences its cost and performance.The positive electrode of the lithium rechargeable battery of researching and developing at present has many series, comprises that mainly the stratiform lithium and cobalt oxides is serial, the laminated Li-Ni oxide is serial, spinel lithium manganese oxide is serial and olivine-type LiFePO4 series.In the said positive electrode, LiCoO 2Because have high electrochemical performance, be widely used as lithium rechargeable battery commercialization positive electrode, but because LiCoO 2In Co belong to scarce resource, cost an arm and a leg, easily environment is polluted, and LiCoO 2Shortcoming such as instability has limited with LiCoO when voltage is higher than 4.3V 2The application of lithium rechargeable battery on hybrid electrically and pure electric automobile as positive electrode; LiNiO 2Poor stability, be prone to cause safety problem, the cation mixing takes place easily and generates the non-stoichiometry structural compounds, and synthetic difficult; LiMn 2O 4The dissolving of crystal transfer, Jahn-Teller effect and manganese ion takes place in recycling process easily, causes with LiMn 2O 4Very fast and high-temperature behavior is undesirable as the decay of the lithium ion secondary battery capacity of positive electrode.Advantage such as the lithium-rich manganese-based trielement composite material Li-Mn-Ni-Co of stratiform has that height ratio capacity, cost are lower, good cycling stability and fail safe are good, and can effectively remedy LiCoO 2, LiNiO 2And LiMn 2O 4Deficiency separately, therefore the exploitation of layered lithium-rich manganese-based trielement composite material becomes the lithium ion secondary battery anode material hot research fields.
But still there is following shortcoming in the lithium-rich manganese-based trielement composite material Li-Ni-Co-Mn of stratiform at present: at first, irreversible capacity is bigger first, and then has influenced the application of said material; Secondly; Because the deposition that the chemical precipitation reaction forms in the preparation process has huge surface energy to contain large quantity of moisture in precipitating, when adopting traditional chamber dryer that said deposition is carried out drying, owing to temperature gradient is low inside and high outside in addition; Can cause the particle in the said deposition agglomeration to occur; Particle size is big, skewness, the performance of the said material that influence prepares.In order to reduce the irreversible capacity first of said material, existing measure mainly is to the modification that coats and mix of said material, as coating Al at said material surface 2O 3, AlPO 4, TiO 2Or V 2O 5Deng and method such as doping C reduce its irreversible capacity first, improve the cycle performance of said material etc.; But mix or be coated in the preparation process trouble of operation, and effect also differs and reserves.
Summary of the invention
Have that particle size is big, particle size distribution is wide and particle agglomeration phenomenon and the bigger defective of irreversible capacity first to the lithium-rich manganese-based ternary composite positive pole of lithium rechargeable battery in the prior art; The object of the present invention is to provide a kind of preparation method of lithium-rich manganese-based ternary composite positive pole; The lithium-rich manganese-based trielement composite material for preparing with said method is as the positive electrode of lithium rechargeable battery, have that granularity is little, particle size distribution evenly, active high, can to reduce first irreversible capacity, improve with said material be the characteristics such as cycle performance of the lithium rechargeable battery of positive electrode.
For realizing above-mentioned purpose, technical scheme of the present invention is following:
A kind of preparation method of lithium-rich manganese-based ternary composite positive pole, said method step is following:
(1) nickel (Ni) salt of solubility, cobalt (Co) salt of solubility and manganese (Mn) salt of solubility are mixed with water, stirring and dissolving evenly obtains mixed solution;
Wherein, said water is that deionized water or purity reach the above water of deionized water purity.
The nickel salt of said solubility can be a kind of in nickel nitrate, nickel acetate, nickelous sulfate or the nickel halogenide (being nickel fluoride, nickel chloride, nickelous bromide, nickel iodide or astatine nickel); The cobalt salt of solubility can be a kind of in cobalt nitrate, cobalt oxalate, cobalt acetate, cobaltous sulfate or the halogenation cobalt (being cobaltous fluoride, cobalt chloride, cobaltous bromide, cobaltous iodide or astatine cobalt); The manganese salt of solubility can be a kind of in manganese nitrate, manganese acetate, manganese sulfate or the manganese halide (being manganous fluoride, manganese chloride, manganous bromide, manganese iodide or astatine manganese); The consumption of the manganese salt of the nickel salt of said solubility, the cobalt salt of solubility and solubility is according to the chemical composition decision of said material; The concentration of metal ions of being made up of nickel ion, cobalt ions and manganese ion in the preferred mixed solution is 0.1mol/L～2.0mol/L.
The mixing time of preferred mixed solution is 1h～6h, and solution temperature is 20 ℃～65 ℃.
(2) get precipitation reagent stirring and dissolving soluble in water, the precipitant solution that obtains clarifying; Mixed solution mixed obtaining reactant liquor with precipitant solution, the pH value of conditioned reaction liquid is 7.0～12.0, stirring reaction, and ageing then refilters and obtains sediment, with washing agent washing and precipitating thing; Sediment after cleaning is cooled to≤-10 ℃, freezing>=1h, under vacuum degree≤10.0Pa, carry out vacuumize then, obtain presoma;
Wherein, said precipitation reagent is a kind of in lithium hydroxide or the carbonic hydroammonium, and consumption is according to the amount decision of the metal ion that needs deposition in the mixed solution.
Said water is that deionized water or purity reach the above water of deionized water purity.
Said washing agent cleans to clean respectively with a kind of cleaning in distilled water, deionized water, absolute ethyl alcohol, ethylene glycol, isopropyl alcohol or the acetone or more than one.
The concentration of preferred precipitant solution is 0.1mol/L～2.5mol/L.
For slowly dripping, rate of addition was 0.002ml/min～48ml/min when preferred mixed solution mixed with precipitant solution.
Preferably with the pH value of ammoniacal liquor and acetic acid conditioned reaction liquid.
Mixing speed during preferred stirring reaction is 100rpm～1000rpm, and the reaction time is 1h～24h; Reaction temperature is 25 ℃～60 ℃.
Preferred digestion time is 1h～24h.
Sediment after preferably will cleaning is cooled to≤and-10 ℃ method is: and the sediment after will cleaning is put into cold-trap, is cooled to-10 ℃～-90 ℃ with cold-trap, and rate of temperature fall is 1～90 ℃/min; Cooling time is 1h～12h.
Sediment after preferably will cleaning is cooled to≤and-10 ℃ method is: condenser temperature reduced to-10 ℃～-90 ℃, the sediment after cleaning in 0 ℃～-20 ℃ refrigerator behind the placement>=1h, put into the freezing 1h～12h of cold-trap after the cooling.
Sediment after preferably will cleaning is cooled to≤and-10 ℃ method is: condenser temperature reduced to-10 ℃～-90 ℃, the sediment after cleaning put into the freezing 1h～12h of cold-trap after the cooling.
The preferred vacuumize time is 1h～24h.
(3) with precursor with heat-treat after lithium salts mixes, obtain a kind of lithium-rich manganese-based ternary composite positive pole of the present invention;
Wherein, said heat treatment temperature is 300 ℃～950 ℃, heat treatment time＞5h;
Said lithium salts can be a kind of in lithium acetate, lithium nitrate, lithium sulfate, lithium halide (lithium fluoride, lithium chloride, lithium bromide, lithium iodide or astatine lithium), lithium hydroxide or the lithium carbonate, and consumption is according to the chemical composition decision of said material;
Mix can be ultrasonic vibration, mortar grinds or the ball mill ball milling in a kind of.
Beneficial effect
1. the preparation method of a kind of lithium-rich manganese-based ternary composite positive pole provided by the invention adopts coprecipitation associating frozen drying method can prepare the lithium-rich manganese-based ternary composite positive pole of primary particle below 50 μ m; In the frozen drying process; Earlier make sediment be in frozen state through refrigerating process; Pass through vacuum treatment then, the liquid in the sediment is removed through distillation, avoided the hole collapse phenomenon that is caused because of the capillary effect of solid liquid interface; The institutional framework and the pore size distribution of dry postprecipitation thing are preserved to greatest extent; Can suppress the generation of particle hard aggregation effectively, obtain the lithium-rich manganese-based ternary composite positive pole of specific area height, particle size distribution homogeneous, said material has higher bulk density and energy density; This makes that the lithium rechargeable battery volume of a constant volume is less relatively, thus reduced said battery cost particularly Vehicular dynamic battery cost and because of the bigger inconvenience that brings of said battery volume;
2. the preparation method of a kind of lithium-rich manganese-based ternary composite positive pole provided by the invention; Decrease with the irreversible capacity first of the said material of preparing, thereby improved the capacity in the follow-up circulation of said battery as the lithium rechargeable battery of positive electrode;
3. the preparation method of a kind of lithium-rich manganese-based ternary composite positive pole provided by the invention, wherein, can be accurately in the coprecipitation process artificial controlled condition obtains target product;
4. the preparation method of a kind of lithium-rich manganese-based ternary composite positive pole provided by the invention; Concentration of reactants, pH value, temperature and charging rate can produce appreciable impact to size, pattern and the chemical property of said material in coprecipitation process; The said material that adopts optimum condition to prepare has layered crystal structure preferably; Even particle distribution, and have higher charge/discharge capacity.
Description of drawings
Fig. 1 is scanning electron microscopy (SEM) figure of the lithium-rich manganese-based ternary composite positive pole for preparing of embodiment 1.
Fig. 2 is scanning electron microscopy (SEM) figure of the lithium-rich manganese-based ternary composite positive pole for preparing of embodiment 1.
Fig. 3 is X-ray diffraction (XRD) figure of the lithium-rich manganese-based ternary composite positive pole for preparing of embodiment 1.
Fig. 4 is the lithium-rich manganese-based ternary composite positive pole for preparing with the embodiment 1 charging and discharging curve figure as the lithium rechargeable battery of positive electrode.
Fig. 5 is the XRD figure of the lithium-rich manganese-based ternary composite positive pole for preparing of embodiment 2.
Fig. 6 is the lithium-rich manganese-based ternary composite positive pole for preparing with the embodiment 2 cyclic voltammetry curve figure as the lithium rechargeable battery of positive electrode.
Embodiment
Following examples are intended to explain the present invention rather than to further qualification of the present invention.
Embodiment 1
(1) nickel acetate of 0.005mol, the cobalt acetate of 0.005mol and the manganese acetate of 0.02mol are dissolved in the 100ml deionized water, stir 4h at 30 ℃ of lower magnetic forces and make it form homogeneous mixed solution, wherein Ni 2+: Co 2+: Mn 2+Amount of substance than for 1:1:4.
(2) lithium hydroxide is dissolved in the lithium hydroxide solution that the deionized water for stirring dissolving obtains the 60ml clarification, wherein the concentration of lithium hydroxide is 1.25mol/L; Mixed solution is added dropwise to mix in the lithium hydroxide solution with the speed of 3ml/min obtains reactant liquor; Using the pH value of ammoniacal liquor conditioned reaction liquid is 11.0; And reactant liquor placed the speed stirring reaction 3h of 50 ℃ of water-baths with 120rmp, and ageing 4h again, suction filtration obtains sediment; Clean 3 times the sediment after obtaining cleaning with distilled water; Sediment after cleaning is put into cold-trap, be cooled to-90 ℃ with cold-trap, rate of temperature fall is 2 ℃/min, behind the freezing 3h, freezing sediment is carried out vacuumize 24h under vacuum degree≤10.0Pa, obtains precursor.
(3) precursor is mixed with lithium hydroxide, wherein, the amount of substance of Li:Ni:Co:Mn is than being 9:1:1:4; With the mortar grinding it is mixed; Get mixture, mixture is first at 480 ℃ of pre-burning 8h with Muffle furnace, be cooled to the room temperature compressing tablet again; In 900 ℃ of sintering 3h, obtain a kind of lithium-rich manganese-based ternary composite positive pole of the present invention then.
It is following that the lithium-rich manganese-based ternary composite positive pole that present embodiment is prepared carries out analytical test:
Fig. 1 and Fig. 2 are the SEM figure of said material, and wherein, Fig. 1 is 2 * 10 4Sem photograph doubly, Fig. 2 is 40 * 10 4Sem photograph doubly can know that by Fig. 1 and Fig. 2 the Dispersion of Particles of said material is even, and particle is formed, shape is identical, and even size distribution is not reunited between the particle; Can know that by Fig. 2 said material particle size is about 200nm.
Fig. 3 is the XRD figure of said material, can be known by figure, about 2 θ=20 ℃, has two very little peaks to occur, and is Li 2MnO 3Characteristic peak, explain that said material has had Li and Mn, the two groups of peaks in (006)/(102) and (108)/(110) splitting degree is apparent in view, and said material complete crystallization is described, crystal formation is perfect.
Through inductance coupling high high-frequency plasma emission spectrometry (ICP-AES) said material is carried out the element test analysis, analysis result shows: the content of lithium (Li), manganese (Mn), nickel (Ni) and cobalt (Co) element is followed successively by 9.101%, 33.07%, 8.25% and 8.44% respectively.
Through above-mentioned structured testing and elementary analysis to said material, the chemical composition that can know said material is Li 1.301Mn 0.610Ni 0.142Co 0.138O 2.191, and have the xLi of being similar to 2MnO 3(1-x) LiNi 1/3Mn 1/3Co 1/3O 2α-NaFeO 4The type layer structure.
Said material and conductive carbon black SP (TIMCAL), binding agent PVDF (5% Kynoar solution) are made into positive plate by mass ratio 8:1:1 smear on aluminium foil, are negative pole with the lithium sheet, and Celgard 2400 makees barrier film, used for electrolyte 1.0mol/L LiPF 6+ ethylene carbonate (EC)+dimethyl carbonate (DMC); Wherein the volume ratio of EC:DMC is 1:1, and to be assembled into model in the glove box of argon gas atmosphere be CR2025 experiment button cell being full of, and on LAND CT2001A tester, tests after leaving standstill 24h; Fig. 4 is the charging and discharging curve figure of said experiment button cell; Can know that by figure the discharging efficiency first of said experiment button cell reaches 74%, discharge and recharge 100 all backs discharge capacities still for about 200mAh/g.
Embodiment 2
(1) nickel acetate of 0.005mol, the cobalt acetate of 0.005mol and the manganese acetate of 0.02mol are dissolved in the 100ml deionized water, stir 2h at 35 ℃ of lower magnetic forces and make it form homogeneous mixed solution, wherein Ni 2+: Co 2+: Mn 2+Amount of substance than for 1:1:4.
(2) the 0.075mol lithium hydroxide is dissolved in the lithium hydroxide solution that the deionized water for stirring dissolving obtains the 60ml clarification, wherein the concentration of lithium hydroxide is 1.25mol/L; Mixed solution is added dropwise to mix in the lithium hydroxide solution with the speed of 5ml/min obtains reactant liquor; Using the pH value of acetate conditioned reaction liquid is 8.0, and reactant liquor is placed the speed stirring reaction 6h of 35 ℃ of water-bath 100rmp, ageing 10h again; Suction filtration obtains sediment; Clean 3 times with distilled water, clean 2 times the sediment after obtaining cleaning again with absolute ethyl alcohol; Earlier condenser temperature is reduced to-90 ℃, the sediment after will cleaning is again put into the cold-trap after the cooling, behind freezing 3h under-90 ℃, freezing sediment is carried out vacuumize 24h under vacuum degree≤10.0Pa, obtains precursor.
(3) precursor is mixed with lithium hydroxide, wherein, the amount of substance of Li:Ni:Co:Mn mixes it than being 9:1:1:4 with the mortar grinding, gets mixture; Mixture is cooled to the room temperature compressing tablet with Muffle furnace is first at 480 ℃ of pre-burning 5h again,, obtains a kind of lithium-rich manganese-based ternary composite positive pole of the present invention then in 900 ℃ of sintering 10h.
Lithium-rich manganese-based ternary composite positive pole to present embodiment prepares is tested as follows:
With said material, the SEM characterization result shows with sem observation: said material granule is evenly distributed, and the groups of grains forming shape is identical, and even size distribution is not reunited between the particle, and said material particle size is about 500nm.
Fig. 5 is the XRD figure spectrum of said material and the XRD figure spectrum basically identical of embodiment 1 gained material, explain said material for rich go up lithium manganese have layer structure and an intact lithium-rich manganese-based ternary composite positive pole of crystal formation.
Through inductance coupling high high-frequency plasma emission spectrometry said material is carried out the element test analysis, analysis result shows: the content of lithium, manganese, nickel and cobalt element is followed successively by 8.746%, 31.32%, 8.22% and 8.13% respectively.
Combine the XRD figure spectrum that the structure and the chemical composition of said material are analyzed again, can know that said material has α-NaFeO 4The type layer structure, chemical composition is: Li 1.262Mn 0.570Ni 0.138Co 0.141O 2.111
With said material and conductive agent carbon black SP (TIMCAL), binding agent PVDF (5% Kynoar solution)) press mass ratio 8:1:1 smear on aluminium foil and make positive plate, be negative pole with the lithium sheet, Celgard 2400 makees barrier film, used for electrolyte 1.0mol/L LiPF 6+ EC+DMC, the volume ratio 1:1 of EC:DMC wherein is assembled into the experiment button cell that model is CR2025 being full of in the glove box of argon gas atmosphere; Said button cell is surveyed its cyclic voltammetry curve on the CHI660c electrochemical workstation, Fig. 6 is the cyclic voltammetry curve figure of embodiment 2 said batteries, as can be seen from the figure, and the main and Ni of the oxidation-reduction process of said material 2+/ Ni 4+, Co 3+/ Co 4+2 redox points are to relevant, the main corresponding Ni in the redox peak of low-pressure area 2+/ Ni 4+, the Co that the higher-pressure region is corresponding 3+/ Co 4+Oxidation-reduction process; And two oxidation peak appear in the initial charge process, and voltage occurs an oxidation peak again during greater than 4.5V, and this is because Li 2MnO 3Existence, the cause that is activated during greater than 4.5V at voltage.The current potential of oxidation peak and reduction peak almost overlaps, and explains that said material invertibity is better.
Embodiment 3
(1) nickel acetate of 0.005mol, the cobalt acetate of 0.005mol and the manganese acetate of 0.02mol are dissolved in the 100ml deionized water, stir 12h at 30 ℃ of lower magnetic forces and make it form homogeneous mixed solution, wherein Ni 2+: Co 2+: Mn 2+Amount of substance than for 1:1:4.
(2) the 2.9372g lithium hydroxide is dissolved in the lithium hydroxide solution that the deionized water for stirring dissolving obtains the 100ml clarification, wherein, OH 1-Be 1.2.1:1 with the amount of substance ratio of metal ion; Mixed solution and lithium hydroxide solution dripped to mix in 60 ℃ beaker with the speed of 10ml/min simultaneously obtain reactant liquor; With the continuous stirring reaction liquid of constant temperature blender with magnetic force, using the pH value of acetic acid conditioned reaction liquid is 8.5, with the speed stirring reaction 3h of 500rmp simultaneously; Ageing 4h again; Suction filtration obtains sediment, washes 3 times the sediment after obtaining cleaning with distilled water; Earlier condenser temperature is reduced to-90 ℃, the sediment after will cleaning is again put into the cold-trap after the cooling, behind freezing 3h under-90 ℃, freezing sediment is carried out vacuumize 24h under vacuum degree≤10.0Pa, obtains precursor.
(3) precursor is mixed with lithium hydroxide, wherein, the amount of substance of Li:Ni:Co:Mn is than being 9:1:1:4; With the mortar grinding it is mixed; Get mixture, mixture is first at 480 ℃ of pre-burning 8h with Muffle furnace, be cooled to the room temperature compressing tablet again; In 900 ℃ of sintering 5h, obtain a kind of lithium-rich manganese-based ternary composite positive pole of the present invention then.
It is following that the lithium-rich manganese-based ternary composite positive pole that present embodiment is prepared carries out analytical test:
Through SEM said material is carried out pattern and characterize, can know the even particle distribution of said material through SEM figure, shape is identical, and even size distribution do not reunite between particle, and said material particle size is about 1 μ m.
Through XRD said material is carried out crystal structure analysis, can know through the XRD figure analysis, said material has two very little peaks to occur about 2 θ=20 ℃, is Li 2MnO 3Characteristic peak, explain that said material has had Li and Mn, the two groups of peaks in (006)/(102) and (108)/(110) splitting degree is apparent in view, and said material complete crystallization is described, crystal formation is perfect.
Through inductance coupling high high-frequency plasma emission spectrometry said material is carried out the element test analysis, can know that said material structure is α-NaFeO 4The type layer structure, chemical composition is: Li 1.308Mn 0.552Ni 0.141Co 0.145O 2.146
Said material and conductive carbon black SP (TIMCAL), binding agent PVDF (5% Kynoar solution) are made into positive plate by mass ratio 8:1:1 smear on aluminium foil, are negative pole with the lithium sheet, and Celgard 2400 makees barrier film, used for electrolyte 1.0mol/L LiPF 6+ ethylene carbonate (EC)+dimethyl carbonate (DMC); Wherein the volume ratio of EC:DMC is 1:1; To be assembled into model in the glove box of argon gas atmosphere be CR2025 experiment button cell being full of, and on LAND CT2001A tester, tests after leaving standstill 20h, and the first discharge specific capacity of said experiment button cell is at 257mAh/g; First charge-discharge efficiency reaches about 80%, discharges and recharges 60 all backs discharge capacities about 190mAh/g.
Embodiment 4
(1) nickel acetate of 0.006mol, the cobalt acetate of 0.006mol and the manganese acetate of 0.018mol are dissolved in the 100ml deionized water, stir 20h at 30 ℃ of lower magnetic forces and make it form homogeneous mixed solution, wherein Ni 2+: Co 2+: Mn 2+Amount of substance than for 1:1:3.
(2) lithium hydroxide is dissolved in the deionized water for stirring dissolving and obtains 100ml clarification lithium hydroxide solution, wherein, the concentration of lithium hydroxide is 0.6mol/L; Mixed solution is added dropwise to mix in the lithium hydroxide solution with the speed of 48ml/min obtains reactant liquor; Using the pH value of ammoniacal liquor conditioned reaction liquid is 11.0; And reactant liquor placed the speed stirring reaction 2h of 50 ℃ of water-baths with 1000rmp, and ageing 10h again, suction filtration obtains sediment; Clean 3 times the sediment after obtaining cleaning with distilled water; Sediment after cleaning is put into refrigerator and cooled earlier freeze 14h, take out and put in advance the cold-trap that is cooled to-90 ℃, fast cooling behind the freezing 5h, under vacuum degree≤10.0Pa carries out vacuumize 20h with freezing sediment to-90 ℃, obtains precursor.
(3) precursor is mixed with lithium hydroxide, wherein, the amount of substance of Li:Ni:Co:Mn is than being 7:1:1:3; With the mortar grinding it is mixed; Get mixture, mixture is first at 480 ℃ of pre-burning 8h with Muffle furnace, be cooled to the room temperature compressing tablet again; In 900 ℃ of sintering 5h, obtain a kind of lithium-rich manganese-based ternary composite positive pole of the present invention then.
It is following that the lithium-rich manganese-based ternary composite positive pole that present embodiment is prepared carries out analytical test:
Said material is carried out the SEM pattern characterize and the XRD structural analysis, can know that through SEM figure said distribution of material is even, the groups of grains forming shape is identical, does not reunite said material particle size even size distribution between the particle.The XRD figure spectrum basically identical of the lithium-rich manganese-based ternary composite positive pole that makes among XRD figure analysis of spectrum through said material and the embodiment 1 is explained lithium manganese on the said material richness, is had layer structure and the intact rich lithium manganese ternary composite positive pole of crystal formation.
Through inductance coupling high high-frequency plasma emission spectrometry said material is carried out element test, can know that said material has α-NaFeO 4The type layer structure, chemical composition is: Li 1.180Mn 0.540Ni 0.180Co 0.177O 2.077
With said material and conductive agent carbon black SP (TIMCAL), binding agent PVDF (5% Kynoar solution)) press mass ratio 8:1:1 smear on aluminium foil and make positive plate, be negative pole with the lithium sheet, Celgard 2400 makees barrier film, used for electrolyte 1.0mol/L LiPF 6+ EC+DMC; The volume ratio 1:1 of EC:DMC wherein; Be assembled into the experiment button cell that model is CR2025 in the glove box of argon gas atmosphere being full of, on LAND CT2001A tester, test after leaving standstill 24h, the first discharge specific capacity of said experiment button cell is at 220mAh/g; Discharge and recharge 50 week back discharge capacities still about 200mAh/g, show better cycle performance and electrochemical stability.
Embodiment 5
(1) nickel acetate of 0.01mol, the cobalt acetate of 0.01mol and the manganese acetate of 0.04mol are dissolved in the 100ml deionized water, stir 4h at 30 ℃ of lower magnetic forces and make it form homogeneous mixed solution, wherein Ni 2+: Co 2+: Mn 2+Amount of substance than for 2:1:8.
(2) carbonic hydroammonium is dissolved in the ammonium bicarbonate soln that the deionized water for stirring dissolving obtains the 100ml clarification, wherein, the concentration of carbonic hydroammonium is 1.25mol/L; Mixed solution and ammonium bicarbonate soln mixed with the speed of 3.5ml/min obtain reactant liquor; Using the pH value of ammoniacal liquor conditioned reaction liquid is 12.0; And reactant liquor placed the speed stirring reaction 3h of 50 ℃ of water-baths with 1000rmp, and ageing 24h again, suction filtration obtains sediment; Clean 3 times the sediment after obtaining cleaning with distilled water; Sediment after cleaning is put into cold-trap, be cooled to-90 ℃ with cold-trap, rate of temperature fall is 5 ℃/min, behind the freezing 3h, freezing sediment is carried out vacuumize 24h under vacuum degree≤10.0Pa, obtains precursor.
(3) precursor is mixed with lithium hydroxide, wherein, the amount of substance of Li:Ni:Co:Mn is than being 17:2:1:8; With the mortar grinding it is mixed; Get mixture, mixture is first at 480 ℃ of pre-burning 8h with Muffle furnace, be cooled to the room temperature compressing tablet again; In 900 ℃ of sintering 5h, obtain a kind of lithium-rich manganese-based ternary composite positive pole of the present invention then.
It is following that the lithium-rich manganese-based ternary composite positive pole that present embodiment is prepared carries out analytical test:
Said material is carried out pattern through SEM characterize, carry out structural analysis through XRD.Can know from SEM result, the even particle spherical in shape of the Dispersion of Particles of said material, particle is formed, shape is identical, and even size distribution is not reunited between the particle, and said material particle size is big slightly, about 5 μ m.Can know about 2 θ=20 ℃, have two very little peaks to occur from XRD figure spectrum, be Li 2MnO 3Characteristic peak, explain that said material has had Li and Mn, the two groups of peaks in (006)/(102) and (108)/(110) splitting degree is apparent in view, and said material complete crystallization is described, crystal formation is perfect.
Through inductance coupling high high-frequency plasma emission spectrometry said material is carried out element test, can know that said material has α-NaFeO 4The type layer structure, chemical composition is: Li 1.220Mn 0.545Ni 0.160Co 0.157O 2.082
Said material and conductive carbon black SP (TIMCAL), binding agent PVDF (5% Kynoar solution) are made into positive plate by mass ratio 8:1:1 smear on aluminium foil, are negative pole with the lithium sheet, and Celgard 2400 makees barrier film, used for electrolyte 1.0mol/L LiPF 6+ ethylene carbonate (EC)+dimethyl carbonate (DMC), wherein the volume ratio of EC:DMC is 1:1, to be assembled into model in the glove box of argon gas atmosphere be CR2025 experiment button cell being full of; On LAND CT2001A tester, test after leaving standstill 24h; Test result shows, said material first discharge capacity about 210mAh/g, first charge-discharge efficiency 70%; Capacity is at 190mAh/g after the circulation of 50 weeks, and cycle performance is good.
Embodiment 6
(1) nickel chloride of 0.005mol, the cobalt chloride of 0.005mol and the manganese nitrate of 0.02mol are dissolved in the 100ml deionized water, stir 3h at 20 ℃ of lower magnetic forces and make it form homogeneous mixed solution, wherein Ni 2+: Co 2+: Mn 2+Amount of substance than for 1:1:4.
(2) 0.004mol carbonic hydroammonium is dissolved in the ammonium bicarbonate soln that the deionized water for stirring dissolving obtains the 60ml clarification, wherein the concentration of carbonic hydroammonium is 0.067mol/L; Mixed solution and ammonium bicarbonate soln be added dropwise to mix in the beaker with 1ml/min speed simultaneously obtain reactant liquor; Using the pH value of ammoniacal liquor conditioned reaction liquid is 7.0; And reactant liquor placed the speed stirring reaction 3h of 35 ℃ of water-baths with 100rmp, and ageing 18h again, suction filtration obtains sediment; Clean 3 times the sediment after obtaining cleaning with distilled water; Sediment after cleaning is put into cold-trap, be cooled to-90 ℃ with cold-trap, rate of temperature fall is 6 ℃/min, behind the freezing 3h, freezing sediment is carried out vacuumize 24h under vacuum degree≤10.0Pa, obtains precursor.
(3) precursor is mixed with lithium hydroxide, wherein, the amount of substance of Li:Ni:Co:Mn is than being 9:1:1:4; With the mortar grinding it is mixed; Get mixture, mixture is first at 480 ℃ of pre-burning 8h with Muffle furnace, be cooled to the room temperature compressing tablet again; In 900 ℃ of sintering 5h, obtain a kind of lithium-rich manganese-based ternary composite positive pole of the present invention then.
It is following that the lithium-rich manganese-based ternary composite positive pole that present embodiment is prepared carries out analytical test:
Utilize SEM that said material pattern is carried out analysis and observation, can know that the Dispersion of Particles of said material is even, particle is formed, shape is identical, does not reunite between the particle, and said material particle size is about 500nm.Utilize XRD that the crystal structure of said material is analyzed; Can know and the XRD figure spectrum basically identical of embodiment 1 gained material through XRD figure spectrum, explain that said material is the rich lithium manganese of going up; Have layer structure, and the intact lithium-rich manganese-based ternary composite positive pole of crystal formation.
Through inductance coupling high high-frequency plasma emission spectrometry said material is carried out element test, get said material and have α-NaFeO 4The type layer structure, chemical composition is: Li 1.250Mn 0.550Ni 0.136Co 0.140O 2.076
Said material and conductive carbon black SP (TIMCAL), binding agent PVDF (5% Kynoar solution) are made into positive plate by mass ratio 8:1:1 smear on aluminium foil, are negative pole with the lithium sheet, and Celgard 2400 makees barrier film, used for electrolyte 1.0mol/L LiPF 6+ ethylene carbonate (EC)+dimethyl carbonate (DMC), wherein the volume ratio of EC:DMC is 1:1, to be assembled into model in the glove box of argon gas atmosphere be CR2025 experiment button cell being full of; On LAND CT2001A tester, test after leaving standstill 24h; Test result shows, said material first discharge capacity about 230mAh/g, first charge-discharge efficiency 75%; Capacity shows excellent cycle performance and electrochemical stability at 200mAh/g after the circulation of 70 weeks.
In sum, more than being merely preferred embodiment of the present invention, is not to be used to limit protection scope of the present invention.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. the preparation method of a lithium-rich manganese-based ternary composite positive pole, it is characterized in that: said method step is following:
(1) soluble nickel, cobalt and manganese salt are mixed with water, stirring and dissolving obtains mixed solution;
(2) get precipitation reagent stirring and dissolving soluble in water, obtain precipitant solution; Mixed solution mixed obtaining reactant liquor with precipitant solution, the pH value of conditioned reaction liquid is 7.0～12.0, stirring reaction, and ageing then refilters and obtains sediment, with washing agent washing and precipitating thing; Sediment after cleaning is cooled to≤-10 ℃, freezing>=1h, under vacuum degree≤10.0Pa, carry out drying then, obtain presoma;
(3) with precursor with heat-treat after lithium salts mixes, obtain a kind of lithium-rich manganese-based ternary composite positive pole;
Wherein, water described in step (1) and (2) is that deionized water or purity reach the above water of deionized water purity;
Precipitation reagent is lithium hydroxide or carbonic hydroammonium described in the step (2); Said washing agent cleans to clean respectively with a kind of cleaning in distilled water, deionized water, absolute ethyl alcohol, ethylene glycol, isopropyl alcohol or the acetone or more than one;
Heat treatment temperature described in the step (3) is 300 ℃～950 ℃, heat treatment time＞5h.
2. the preparation method of a kind of lithium-rich manganese-based ternary composite positive pole according to claim 1 is characterized in that: soluble nickel salt is nickel nitrate, nickel acetate, nickelous sulfate or nickel halogenide described in the step (1); The solubility cobalt salt is cobalt nitrate, cobalt oxalate, cobalt acetate, cobaltous sulfate or halogenation cobalt; Soluble manganese salt is manganese nitrate, manganese acetate, manganese sulfate or manganese halide.
3. the preparation method of a kind of lithium-rich manganese-based ternary composite positive pole according to claim 1 is characterized in that: in the mixed solution, the concentration of metal ions of being made up of nickel, cobalt and manganese ion is 0.1mol/L～2.0mol/L described in the step (1).
4. the preparation method of a kind of lithium-rich manganese-based ternary composite positive pole according to claim 1 is characterized in that: the mixing time of mixed solution is 1h～6h described in the step (1), and solution temperature is 20 ℃～65 ℃.
5. the preparation method of a kind of lithium-rich manganese-based ternary composite positive pole according to claim 1 is characterized in that: the concentration of precipitant solution is 0.1mol/L～2.5mol/L described in the step (2).
6. the preparation method of a kind of lithium-rich manganese-based ternary composite positive pole according to claim 1 is characterized in that: for slowly dripping, rate of addition was 0002ml/min～48ml/min when mixed solution mixed with precipitant solution in the step (2).
7. the preparation method of a kind of lithium-rich manganese-based ternary composite positive pole according to claim 1 is characterized in that: the mixing speed during stirring reaction described in the step (2) is 100rpm～1000rpm, and the reaction time is 1h～24h; Reaction temperature is 25 ℃～60 ℃; Digestion time is 1h～24h.
8. the preparation method of a kind of lithium-rich manganese-based ternary composite positive pole according to claim 1; It is characterized in that: the sediment after will cleaning is cooled to≤and-10 ℃ method is: and the sediment after 1. will cleaning is put into cold-trap; Be cooled to-10 ℃～-90 ℃ with cold-trap; Rate of temperature fall is 1～90 ℃/min, and cooling time is 1h～12h; Or 2. condenser temperature is reduced to-10 ℃～-90 ℃, the sediment after cleaning in 0 ℃～-20 ℃ refrigerator behind the placement>=1h, is put into the freezing 1h～12h of cold-trap after the cooling; Or 3. condenser temperature is reduced to-10 ℃～-90 ℃, the sediment after cleaning is put into the freezing 1h～12h of cold-trap after the cooling.
9. the preparation method of a kind of lithium-rich manganese-based ternary composite positive pole according to claim 1 is characterized in that: the vacuumize time is 1h～24h.
10. the preparation method of a kind of lithium-rich manganese-based ternary composite positive pole according to claim 1 is characterized in that: lithium salts is lithium acetate, lithium nitrate, lithium sulfate, lithium halide, lithium hydroxide or lithium carbonate described in the step (3).
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