CN104241631B - A kind of lithium ion battery high power capacity positive electrode - Google Patents

A kind of lithium ion battery high power capacity positive electrode Download PDF

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Publication number
CN104241631B
CN104241631B CN201410449554.XA CN201410449554A CN104241631B CN 104241631 B CN104241631 B CN 104241631B CN 201410449554 A CN201410449554 A CN 201410449554A CN 104241631 B CN104241631 B CN 104241631B
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lithium
positive electrode
high power
power capacity
capacity
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CN104241631A (en
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郭玉国
石吉磊
江柯成
卿任鹏
万立骏
张亚利
李明文
张风太
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Shandong Wina Green Power Technology Co ltd
Wuhe Power Technology Co ltd
Institute of Chemistry CAS
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Shandong Wina Green Power Technology Co ltd
Wuhe Power Technology Co ltd
Institute of Chemistry CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of preparation method of high power capacity positive electrode.This method comprises the steps：1) transition metal salt solution, aqueous slkali, the bottom liquid of specific ion intensity are prepared；2) control stir speed (S.S.), pH, reaction temperature, both the above solution is added in reactor and is aged；3) lithium salts is dissolved in ultra-pure water wiring solution-forming, spherical precursor is added into lithium salt solution stirring Hybrid Heating makes water volatilization, dry, calcining obtain high power capacity positive electrode 0.5Li2MnO3·0.5LiNi1/3Co1/3Mn1/3O2.Method by controlling bottom liquid ionic strength, controls precipitation reaction speed, and the nucleation and growth speed of control crystal forms it into the spherical precursor of uniform, controllable.And the present invention reaches presoma and the mixed uniformly purpose of lithium salts by material by wet type mixing, be conducive to the high power capacity positive electrode of calcining generation excellent performance.

Description

A kind of lithium ion battery high power capacity positive electrode
Technical field
The present invention relates to a kind of preparation method of lithium ion battery with lithium-rich positive electrode.
Background technology
Lithium ion battery is because with operating voltage is high, specific energy is high, capacity is big, self discharge is small, cyclicity good, service life The outstanding advantages such as long, environment-friendly, lightweight, small volume and be widely used in mobile electronic device, pen as ideal source Remember the portable electric appts such as this computer.At the same time, with the high speed development of society, the exhaustion of petroleum resources, environmental pressure Etc. factor, hybrid power and pure electric automobile will turn into the main flow of future transportation instrument, and this is also just to large-sized power lithium ion Battery proposes higher requirement.Exploitation high power capacity, high power density, the lithium ion battery of good cycling stability, which turn into, at present grinds The emphasis and focus studied carefully, wherein the positive electrode of exploitation high power capacity is urgently to be resolved hurrily as the bottleneck problem studied at present.
Its positive electrode of the lithium ion battery still predominantly cobalt acid lithium (LiCoO largely commercially produced at present2).The material A large amount of cobalts expensive using natural abundance low price, the toxicity of cobalt is big in addition, there is serious potential safety hazard under the conditions of overcharging. Although the nickel-cobalt-manganese ternary material grown up at present has preferable cyclical stability, specific capacity is difficult more than 200mAh g-1, it is very difficult to meet demand of the following electric automobile to electrokinetic cell.And with stratiform similar with cobalt acid lithium, nickel-cobalt-manganese ternary material The manganese base lithium-rich anode material of structure turns into " star " material and obtained due to the specific capacity with superelevation and relatively low cost of material To extensive concern and research.
The main still 0.5Li of current lithium-rich manganese-based layered cathode material2MnO3·0.5LiNi1/3Co1/3Mn1/3O2, solid solution (or blending) material.Specific capacity alreadys exceed 250mAh g under its current document report room temperature low range-1, but high rate performance and Cyclical stability is to be improved.The synthesis of lithium-rich manganese-based layered cathode material is molten mainly with collosol and gel and coprecipitation method The raw material that gelling gluing method is used is acetate, and raw material is expensive compared to the sulfate that co-precipitation is used, in addition sol-gal process The material primary particle particle diameter of synthesis is small, and specific surface area is big, cyclical stability is poor.And the material of coprecipitation method synthesis is mainly There is micro-nano compound structure by the closelypacked spherical micron order second particle of nanoscale primary particle, therefore material has preferably Cyclical stability.
The content of the invention
The purpose of the present invention be prepare particle diameter by controlling to adjust the method for coprecipitation reaction bottom liquid ionic strength can Control and homogeneous lithium-rich manganese-based layered cathode material spherical precursor, and invented and realize that lithium salts is equal with presoma using solwution method The method for mixing of even batch mixing, final high-temperature calcination obtains the lithium-rich manganese-based layered cathode material of superior performance.
The specific implementation method provided by the present invention for preparing lithium ion battery high power capacity positive electrode, including following steps Suddenly：
(1) preparation of solution：Compound concentration is 0.1-5mol/L transition metal salt solution, preferably 0.5- respectively 3mol/L, compound concentration is 0.1-5mol/L sodium carbonate or sodium hydroxide solution, preferably 0.5-3mol/L, compound concentration For 0.1-5mol/L ammonia spirit, preferred concentration be 0.1-2mol/L (wherein in transition metal solution the proportioning of nickel cobalt manganese by The nickel cobalt manganese proportioning designed in product determines that the alkali used may be selected from NaCO3, any one in NaOH)
(2) preparation of bottom liquid：Concentration ranges 0.1-5mol/L metabisulfite solution, preferred concentration 0.8-1.5mol/L with it is dense Spend interval 0.1-5mol/L ammonia spirit, the ionic strength of preferred concentration 0.5-1.5mol/L mixing regulation bottom liquid.According to from Sub- strength calculation formula I=1/2 (b1z1 2+b2z2 2+ ...), wherein I is ionic strength, and b is the molality of each ion, z For the charge number of each ion.The interval of bottom liquid ionic strength is 0.3-15mol/L, and preferably liquid ionic strength in bottom is 3-7.5mol/ L。
(3) synthesis of presoma：The bottom liquid 1-20L prepared in (2) is added in coprecipitation reaction kettle and is heated to temperature Interval 50-60 DEG C, adjust depending on reactor rotating speed interval 600-1000r/min, the suitable reactor volume of the addition volume of bottom liquid and be The 1/3-1/2 of reactor cumulative volume.Using peristaltic pump with the interval pump speed for 10-1000mL/h of pump speed, by the mistake of configuration in (1) Cross metallic solution, alkali lye (NaCO3, NaOH solution), ammonia spirit is added in reactor and controls pH stable in interval jointly PH8-11, wherein transition metal solution and alkali lye NaCO3Ratio be 1:1 if alkali lye is NaOH ratios is 1:2, ammoniacal liquor The ratio of consumption and alkali lye is 0.2-1.Charging keeps the temperature-resistant digestion time interval 1-12h of rotating speed after terminating.After the completion of ageing The mixing and calcining for being precipitated to milli-Q water and (4) presoma and lithium salts thoroughly being dried in neutrality, 80-100 DEG C of baking oven are filtered, To design, the mol ratio of product weighs the presoma of synthesis in (3), (lithium salts excess 5%-20%, lithium salts can be LiOH to lithium salts Or Li2CO3), lithium salts is dissolved in ultra-pure water, then added the presoma weighed in lithium salt solution under slow stirring, is stirred Time is 5-30min, and heating-up temperature is 80-100 DEG C, is volatilized completely to water, in 80-120 DEG C of thoroughly drying of oven temperature.Will The sample of drying is calcined with certain calcination condition, with 1-10 DEG C/min heating rate temperature programming, is forged at 700-1000 DEG C Burn, be incubated 10-30h.Alternately, with 1-10 DEG C/min heating rate temperature programming, in 400-500 DEG C of preferred insulation 3- 7h, continuation preferably is preferably warming up to 750-950 DEG C, is preferably incubated 10-20h with heating rate 3-7 DEG C/min temperature programmings, Finally give product.
The present invention provides a kind of preparation method of high capacity cathode material of lithium ion battery, using the method for co-precipitation, altogether The method of precipitation can use following ionic reaction formula to represent：
(1)M2++SO4 2-+nNH3·H2O→[M(NH3)n]2++SO4 2-+nH2O
(2)[M(NH3)n]2++SO4 2-+2Na++CO3 2-+nH2O→MCO3↓+SO4 2-+2Na++nNH3·H2O
(wherein M2+For Ni2+,Co2+,Mn2+；Sodium carbonate is alternatively sodium hydroxide etc.) by molten knowable to above reaction equation (1) (2) Ionic strength in liquid has material impact to above-mentioned reaction rate, understands that solid exists by Ostwald crystal growths curing mechanism Precipitation in solution is the nucleation rate v of crystal1=k (Q-s)/s and nucleus growth rate v2=DA (Q-s)/δ all with it is above-mentioned React the closely related too fast v of precipitation of (2) speed1It is far longer than v2Generate a large amount of nucleus and be unfavorable for balling-up, crystal growth rate v2Cross Big ball presoma is formed soon.Therefore by adjust control bottom liquid ionic strength, control reaction (2) speed come control crystal nucleation with The speed of growth successfully synthesizes the homogeneous controllable spherical micron presoma of particle diameter distribution, overcomes particle diameter point in precursor synthesis The problem of cloth is uneven.In addition presoma and lithium salts are successfully realized the invention provides a kind of presoma and lithium salts hybrid mode Uniform mixing, greatly enhances the performance of final calcined product.The high power capacity lithium-rich anode material prepared using this method Expect for the primary particle less than 300nm it is tightly packed into homogeneous micron order micro-nano complex bulb structure, under low range 0.05C Specific capacity is more than 250mAhg-1, with preferable high rate performance, have under 2C more than 150mAhg-1Specific capacity, stable circulation Property it is good, 70 circulation after capacity attenuation be less than 5%, in addition by 70 circulate after voltage attenuation be less than 0.2V.Chemical property The material synthesized better than other method.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum (XRD) of high-capacity lithium-rich cathode material in embodiment 1.
Fig. 2,3 be embodiment 1 in high-capacity lithium-rich cathode material electron scanning micrograph.
Fig. 4 be embodiment 1 in high-capacity lithium-rich cathode material as anode material for lithium-ion batteries, under 0.05C multiplying powers Discharge curve.
Fig. 5 is the circulation of high-capacity lithium-rich cathode material 70 circles under 0.2C in embodiment 1.
Fig. 6 is the charging and discharging curve of high-capacity lithium-rich cathode material the 10th circle and the 70th circle under 0.2C in embodiment 1.
Embodiment
With reference to specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Experimental method described in following embodiments, is conventional method unless otherwise specified；The reagent and material, such as Without specified otherwise, commercially obtain.
Embodiment 1：
2mol/L transition metal salt solutions 1L is configured at 25 DEG C of room temperature：Manganous sulfate monohydrate 1.34mol, six hydration nickel sulfate 0.33mol, Cobalt monosulfate heptahydrate 0.33mol add ultra-pure water to be made into volume 1L transition metal salt solution；Configure 2mol/L carbon Acid sodium solution 1L：Natrium carbonicum calcinatum 2mol adds ultra-pure water to be made into volume 1L solution, adds in the Carbon Dioxide sodium solution of configuration Commercially available ammoniacal liquor 15ml (concentration is 0.5mol/L).Bottom liquid configures 1mol/L metabisulfite solution：284g (2mol) sodium sulphate adds super Pure water is made into 2L solution, adds in 5L automatic control reactors, and it is 8.5 that ammoniacal liquor regulation pH, which is added dropwise, and now the ionic strength of bottom liquid is 3mol/L, reactor rotational speed regulation be 800 revs/min, temperature setting be 60 DEG C, control pH be 8.5 it is constant under conditions of with The above-mentioned transition metal salt solution prepared and sodium carbonate liquor are passed through in reactor by 500ml/h charging rate, lead to material reaction 1h, stops thoroughly drying 5 in logical material reaction aging 5h, taking-up reaction product filtering milli-Q water to neutrality, 100 DEG C of baking ovens My god, obtain presoma.Weigh 50g lithium carbonates add water 500ml dissolving, then add 100g presoma stir 30 minutes, heat 100 DEG C All volatilize, thoroughly dried 1 day in 100 DEG C of baking ovens to water, be transferred to 450 DEG C of calcining 5h in Muffle furnace, then be warming up to 850 DEG C of calcinings 12h, is cooled to room temperature and obtains high-capacity lithium-rich cathode material.
The sign of high-capacity lithium-rich cathode material：
With powder x-ray diffraction (Rigaku DmaxrB, CuKαRay) analysis high-capacity lithium-rich cathode material crystal Structure.As a result it is as shown in Figure 1.As can be seen from the figure material meets the crystal peak of rich lithium material, has no miscellaneous peak and illustrates that material is pure Degree is higher, and 003/104 peak is more than 1.2 and shows that the peak between cation mixing, 20 ° to 25 ° is not present in orderly ion arrangement Illustrate Li2MnO3The presence of phase superlattices.
The pattern of the high-capacity lithium-rich cathode material and presoma is characterized with SEM (JEOL-6700F), As shown in Figure 2,3.As seen from the figure, rich lithium material and presoma are all that particle diameter distribution is uniformly spherical, finally calcine obtained height Capacity lithium-rich anode material be once nanometer little crystal grain it is tightly packed into big micron ball, with preferable micro-nano composite junction Structure.
The Electrochemical Characterization of high-capacity lithium-rich cathode material：
By the high-capacity lithium-rich cathode material prepared in embodiment 1, acetylene black and Kynoar binding agent with matter Amount compares 80：10：10 mixing are made into slurry, are homogeneously applied to obtain positive pole diaphragm in aluminum foil current collector.Using metal lithium sheet as Negative pole, microporous polypropylene membrane (Celgard2400) is used as barrier film, 1mol/L LiPF6(solvent is that volume ratio is 1：1 ethylene Alkene ester and dimethyl carbonate mixed liquor) as electrolyte, it is assembled into button cell in the glove box that argon gas is protected.
The battery of above-mentioned assembling is subjected to constant current charge-discharge test on blue electric charge-discharge test instrument, charge-discharge magnification is 0.05C, charging/discharging voltage interval is 2-4.8V.The discharge curve of the 1st time is as shown in figure 4, the high power capacity is rich as seen from the figure The discharge capacity of lithium anode material is up to 250mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circles Circulate (as shown in Figure 5), the high-capacity lithium-rich cathode material has preferable cyclical stability as seen from the figure, by 70 circles Circulation after also have 198mAh/g specific capacity, capacity attenuation 2%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2- 4.8V, the charging and discharging curve of the 10th circle and the 70th circle as shown in fig. 6, material has less voltage attenuation as seen from the figure, Average voltage decays to 0.18V.
Embodiment 2：
The concentration of sodium sulphate is 1.5mol/L in the liquid of bottom, and the concentration of ammoniacal liquor is 1mol/L, and the ionic strength of bottom liquid is 4.5mol/L, it is other same as Example 1.The presoma of synthesis still keeps spherical morphology.
Button cell is assembled into using technique same as Example 1.Charge-discharge magnification is 0.05C, charging/discharging voltage area Between be 2-4.8V.Discharge capacity is up to 242mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circles Circulation also has 180mAh/g specific capacity, capacity attenuation 3.8%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2- 4.8V, the 10th circle decays to 0.25V with the 70th average voltage.
Embodiment 3：
The concentration of sodium sulphate is 0.5mol/L in the liquid of bottom, and the concentration of ammoniacal liquor is 1mol/L, and the ionic strength of bottom liquid is 1.5mol/L, it is other same as Example 1.Gained presoma pattern is uneven.
Button cell is assembled into using technique same as Example 1.Charge-discharge magnification is 0.05C, charging/discharging voltage area Between be 2-4.8V.Discharge capacity is up to 235mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circles Circulation also has 172mAh/g specific capacity, capacity attenuation 4.5%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2- 4.8V, the 10th circle decays to 0.35V with the 70th average voltage.
Embodiment 4：
The concentration of sodium sulphate is 3.0mol/L in the liquid of bottom, and the concentration of ammoniacal liquor is 1mol/L, and the ionic strength of bottom liquid is 9mol/ L, it is other same as Example 1.Gained presoma pattern is uneven.
Button cell is assembled into using technique same as Example 1.Charge-discharge magnification is 0.05C, charging/discharging voltage area Between be 2-4.8V.Discharge capacity is up to 250mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circles Circulation also has 178mAh/g specific capacity, capacity attenuation 7.3%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2- 4.8V, the 10th circle decays to 0.52V with the 70th average voltage.
Embodiment 5：
The concentration of sodium sulphate is 3.0mol/L, and the concentration of ammoniacal liquor is 2mol/L, the ionic strength of bottom liquid for 9mol/L (, its It is same as Example 1.Gained presoma pattern is uneven.
Button cell is assembled into using technique same as Example 1.Charge-discharge magnification is 0.05C, charging/discharging voltage area Between be 2-4.8V.Discharge capacity is up to 220mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circles Circulation also has 178mAh/g specific capacity, capacity attenuation 5.8%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2- 4.8V, the 10th circle decays to 0.45V with the 70th average voltage.
Embodiment 6：
The concentration of sodium sulphate is 0.8mol/L, and the concentration of ammoniacal liquor is 0.6mol/L, and the ionic strength of bottom liquid is 2.4mol/L, It is other same as Example 1.Resulting presoma pattern is uneven.
Button cell is assembled into using technique same as Example 1.Charge-discharge magnification is 0.05C, charging/discharging voltage area Between be 2-4.8V.Discharge capacity is up to 238mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circles Circulation also has 189mAh/g specific capacity, capacity attenuation 4.2%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2- 4.8V, the 10th circle decays to 0.38V with the 70th average voltage.
Embodiment 7：
The concentration of sodium sulphate is 1mol/L, and the concentration of ammoniacal liquor is 1mol/L, and the ionic strength of bottom liquid is 3mol/L, change into Material speed is 50ml/h, other same as Example 1.Resulting presoma pattern not balling-up and uneven.
Button cell is assembled into using technique same as Example 1.Charge-discharge magnification is 0.05C, charging/discharging voltage area Between be 2-4.8V.Discharge capacity is up to 220mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circles Circulation also has 159mAh/g specific capacity, capacity attenuation 8.2%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2- 4.8V, the 10th circle decays to 0.7V with the 70th average voltage.
Embodiment 8：
The concentration of sodium sulphate is 1mol/L, and the concentration of ammoniacal liquor is 1mol/L, and the ionic strength of bottom liquid is 3mol/L, change into Material speed is 100ml/h, other same as Example 1.Resulting presoma pattern not balling-up and uneven.
Button cell is assembled into using technique same as Example 1.Charge-discharge magnification is 0.05C, charging/discharging voltage area Between be 2-4.8V.Discharge capacity is up to 228mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circles Circulation also has 163mAh/g specific capacity, capacity attenuation 7.8%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2- 4.8V, the 10th circle decays to 0.68V with the 70th average voltage.
Embodiment 9：
The concentration of sodium sulphate is 1mol/L, and the concentration of ammoniacal liquor is 1mol/L, and the ionic strength of bottom liquid is 3mol/L, change into Material speed is 200ml/h, other same as Example 1.Resulting presoma pattern balling-up but sphere diameter skewness.
Button cell is assembled into using technique same as Example 1.Charge-discharge magnification is 0.05C, charging/discharging voltage area Between be 2-4.8V.Discharge capacity is up to 230mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circles Circulation also has 175mAh/g specific capacity, capacity attenuation 7.4%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2- 4.8V, the 10th circle decays to 0.5V with the 70th average voltage.
Embodiment 10：
The concentration of sodium sulphate is 1mol/L, and the concentration of ammoniacal liquor is 1mol/L, and the ionic strength of bottom liquid is 3mol/L, change into Material speed is 350ml/h, other same as Example 1.Resulting presoma pattern balling-up, uniform sphere diameter distribution.
Button cell is assembled into using technique same as Example 1.Charge-discharge magnification is 0.05C, charging/discharging voltage area Between be 2-4.8V.Discharge capacity is up to 230mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circles Circulation also has 178mAh/g specific capacity, capacity attenuation 7.1%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2- 4.8V, the 10th circle decays to 0.45V with the 70th average voltage.
Embodiment 11：
The concentration of sodium sulphate is 1mol/L, and the concentration of ammoniacal liquor is 1mol/L, and the ionic strength of bottom liquid is 3mol/L, change into Material speed is 1000ml/h, other same as Example 1.Resulting presoma pattern balling-up, uniform sphere diameter distribution.
Button cell is assembled into using technique same as Example 1.Charge-discharge magnification is 0.05C, charging/discharging voltage area Between be 2-4.8V.Discharge capacity is up to 228mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circles Circulation also has 182mAh/g specific capacity, capacity attenuation 5.3%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2- 4.8V, the 10th circle decays to 0.47V with the 70th average voltage.
Embodiment 12：
The concentration of sodium sulphate is 1mol/L, and the concentration of ammoniacal liquor is 1mol/L, and the ionic strength of bottom liquid is 3mol/L, change into Material speed is 2000ml/h, other same as Example 1.Resulting presoma pattern not balling-up, and skewness.
Button cell is assembled into using technique same as Example 1.Charge-discharge magnification is 0.05C, charging/discharging voltage area Between be 2-4.8V.Discharge capacity is up to 240mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circles Circulation also has 165mAh/g specific capacity, capacity attenuation 10.1%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2- 4.8V, the 10th circle decays to 0.87V with the 70th average voltage.
Comparative example 1：
Other same as Example 1, difference is：Material by wet type mixing is not used, presoma is mixed with lithium salts, then one Ball milling for a period of time, is subsequently placed in calcining in Muffle furnace in fixed ball-milling medium.
Then button cell is assembled into using technique same as Example 1.Charge-discharge magnification is 0.05C, discharge and recharge electricity It is 2-4.8V between nip.Discharge capacity is up to 200mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circle circulations also have 160mAh/g specific capacity, capacity attenuation 3.2%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, the 10th circle decays to 0.5V with the 70th average voltage.
Comparative example 2：
Other same as Example 1, difference is：Bottom liquid does not add sodium sulphate and ammoniacal liquor regulation ionic strength.
Then button cell is assembled into using technique same as Example 1.Charge-discharge magnification is 0.05C, discharge and recharge electricity It is 2-4.8V between nip.Discharge capacity is up to 218mAh/g.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2-4.8V, 70 circle circulations also have 160mAh/g specific capacity, capacity attenuation 8%.Charge-discharge magnification is 0.2C, and charging/discharging voltage interval is 2- 4.8V, the 10th circle decays to 0.83V with the 70th average voltage.
Comparison by embodiment 1 and comparative example 1 is visible, and lithium ion cell positive can be significantly improved using material by wet type mixing The discharge capacity of material, capacity attenuation and average voltage attenuation after reduction circulation.
Comparison by embodiment 2 and comparative example 2 is visible, and adding sodium sulphate and ammoniacal liquor regulation ionic strength can substantially carry The discharge capacity of high-lithium ion cell positive material, capacity attenuation and average voltage attenuation after reduction circulation.
Comparison by embodiment 1-4 is visible, and the concentration of sodium sulphate is preferred interval for 0.8-1.5mol/L, gained lithium ion Capacity attenuation is smaller after the circulation of cell positive material, and average voltage decay is smaller；By embodiment 2,5-6 comparison is visible, The concentration of ammoniacal liquor is preferred interval for 0.5-1.5mol/L, capacity attenuation after the circulation of the anode material for lithium-ion batteries now obtained It is smaller with voltage attenuation.

Claims (2)

1. a kind of high power capacity positive electrode 0.5Li2MnO3·0.5LiNi1/3Co1/3Mn1/3O2Preparation method, its
It is characterised by comprising the following steps：
1) according to Ni:Co:Mn is 1:1:4 molar ratio prepares 0.1-5mol/L transition metal salt solution, prepares 0.1- 5mol/L sodium carbonate or sodium hydroxide solution, the ammonia spirit for preparing 0.1-5mol/L, preparation ionic strength are 3-7.5mol/ L Na2SO4With NH3·H2O mixing bottom liquid；
2) by the transition metal salt solution prepared, sodium carbonate or sodium hydroxide solution and ammonia spirit with 350ml-1000ml/h's Feed rate is passed through in reactor at 50-60 DEG C of the rotating speed and temperature of 700-1000 revs/min of stir speed (S.S.) so that in reactor PH reach 8-11, and be aged 1-20h, precipitation takes out washing, dries；
3) batch mixing is calcined, by the lithium salts measured than weighing excessive ratio, adds ultra-pure water dissolving, by metering than adding presoma stirring Mixing, by water volatile dry, then temperature programming and is incubated, finally gives high power capacity positive electrode.
2. the preparation method of high power capacity positive electrode as claimed in claim 1, it is characterised in that：Transition metal salt solution is selected from Nickel sulfate, cobaltous sulfate, manganese sulfate, lithium salts are selected from lithium hydroxide, lithium carbonate, lithium nitrate.
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