CN105070907B - A kind of nickelic positive electrode and preparation method thereof and lithium ion battery - Google Patents

A kind of nickelic positive electrode and preparation method thereof and lithium ion battery Download PDF

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CN105070907B
CN105070907B CN201510545968.7A CN201510545968A CN105070907B CN 105070907 B CN105070907 B CN 105070907B CN 201510545968 A CN201510545968 A CN 201510545968A CN 105070907 B CN105070907 B CN 105070907B
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positive electrode
compound
solution
nickelic positive
nickel
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CN201510545968.7A
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CN105070907A (en
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于建
佘圣贤
袁徐俊
陈涨宗
温美盛
罗江鲲
应皆荣
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宁波容百新能源科技股份有限公司
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    • H—ELECTRICITY
    • H01—BASIC 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—BASIC 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—BASIC 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—BASIC 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
    • H—ELECTRICITY
    • H01—BASIC 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Abstract

The present invention provides a kind of nickelic positive electrode, including：Matrix, described matrix surface doping have Al, Ti, Mg, Zr, Ca, Zn, B, F, V, Sr, Ba, Y, Nd, Cs, W, Mo, Ru, Rd or lanthanide series；The clad on described matrix surface is coated on, contains one or more of magnesium, titanium, zirconium, fluorine, boron, aluminium and phosphate radical in the clad.Nickelic positive electrode matrix surface provided by the invention contains doped chemical, the element of doping being capable of stabilized matrix surface crystal structure, alleviate cleaning solution to substrate material surface structural damage, make the capacity of lithium ion battery of nickelic positive electrode preparation and cycle performance preferable.In addition, this nickelic positive electrode carries clad, clad can be such that positive electrode isolates with anolyte portion, improve the electrochemical stability and security of positive electrode.The present invention also provides a kind of preparation methods and lithium ion battery of nickelic positive electrode.

Description

A kind of nickelic positive electrode and preparation method thereof and lithium ion battery

Technical field

The present invention relates to positive electrode technical field more particularly to a kind of nickelic positive electrode and preparation method thereof and lithium from Sub- battery.

Background technology

Now, the importance of energy storage technology is increasingly prominent, makes rechargeable type lithium ion battery (LIBs) gradually in electronics Consumer field of power supplies occupies leading position.Lithium ion battery has energy storage densities high, and security is good, charge-discharge magnification The advantages of height, maintenance cost is relatively low and service life is longer, lithium ion battery is widely used in daily life.

In the research application field of anode material for lithium-ion batteries, stratiform transition metal oxide by extensive concern, wherein LiCoO2Obtained in the application of small-scale lithium ion cell compared with ten-strike, but the security of this battery and thermal stability compared with Difference limits its extensive use；LiNiO2Structure feature and LiCoO2It is basically identical, but pure phase LiNiO2Material is not easy to make It is standby, and lithium and nickel ion are present with mixing phenomenon in its crystal structure, so as to cause the reduction of battery performance, therefore LiNiO2Larger limitation is received as positive electrode application；In order to overcome the above problem, researchers pass through in nickel ion layer It is middle to mix other metal ions (Co, Mn, Al, Mg etc.) to improve its electrochemical stability；Nickelic positive electrode after doping LiNi1-xMxO2(M Co, Mn, Al, Ti etc.) not only has higher capacity and excellent cycle performance, and security performance also obtains Improve；But the surface residual alkali content of this nickelic anode ternary material is compared with LiCoO2It is higher, and with Ni contents Raising, surface residual alkali amount increase, residual alkali is mainly with Li2O、Li2CO3, the forms such as LiOH exist, alkaline matter pole in air Moisture-sensitive absorbs water, and nickelic positive electrode surface is made to be reacted with water, and positive electrode viscosity when sizing mixing is caused to become larger or even coagulate Glue brings extra moisture in battery into, increases lithium salts amount in battery, and generation side reaction in battery is caused to make the internal resistance of cell Become larger, the capacity and cycle performance for causing battery decline, it is also possible to battery be made flatulence phenomenon occur.

The surface simplest method of residual alkali amount for reducing above-mentioned nickelic positive electrode is to increase washing step in preparation process Suddenly；But during nickelic positive electrode washing is prepared, material surface is very sensitive to moisture, and chemical lithium deintercalation easily occurs Reaction, causes the destruction of material surface crystal structure, so that capacity of lithium ion battery and cycle performance prepared by positive electrode It is poor.

The content of the invention

In view of this, it is an object of the invention to provide a kind of nickelic positive electrode and preparation method thereof and lithium-ion electrics Pond, the lithium ion battery that nickelic positive electrode provided by the invention is prepared have preferable capacity and cycle performance.

The present invention provides a kind of nickelic positive electrode, including：

Matrix, the preparation method of described matrix are：

It is calcined after the compound of nickel cobalt, lithium compound and doping element compound are mixed, obtains matrix, the nickel cobalt It is the oxide that Formulas I compound represented or Formulas I compound represented are obtained through peroxidating to close object：

Ni1-x-yCoxMy(OH)2Formulas I,

In Formulas I, 0.05≤x≤0.30,0.01≤y≤0.20, in M Mn, Al, Ti, Mg, Zr, Ca, Zn, Sr, La and B One or more；

Doped chemical in the doping element compound is Al, Ti, Mg, Zr, Ca, Zn, B, F, V, Sr, Ba, Y, Nd, One or more of Cs, W, Mo, Ru, Rd and lanthanide series；

The molal quantity and the ratio of the molal quantity of Li that the nickel cobalt compound and the dosage of lithium compound make Ni, Co and M total For 1:(0.9~1.15)；

The clad on described matrix surface is coated on, contains magnesium, titanium, zirconium, fluorine, boron, aluminium and phosphate radical in the clad One or more of.

Preferably, the quality of the doping element compound is the 0.5%~1% of the compound quality of nickel cobalt.

Preferably, the quality of the clad be substrate quality B%, 0 ＜ B≤5.

Nickelic positive electrode matrix surface provided by the invention contains doped chemical, and the element of doping being capable of stabilized matrix table Faceted crystal structure alleviates cleaning solution to substrate material surface structural damage, the lithium ion that nickelic positive electrode is prepared Battery capacity and cycle performance are preferable.The experimental results showed that the button electricity that nickelic positive electrode provided by the invention is prepared 25 DEG C of pond, 0.1C first discharge specific capacities reach 194mAh/g~204mAh/g；50 weeks capacity retention ratio ＞ of 1C charge and discharge cycles 96%.

In addition, nickelic positive electrode provided by the invention carries clad, clad can make positive electrode and electrolyte Part isolates, and improves the electrochemical stability and security of positive electrode.

The present invention provides a kind of preparation method of nickelic positive electrode described in above-mentioned technical proposal, including：

It is calcined after the compound of nickel cobalt, lithium compound and doping element compound are mixed, obtains matrix, the nickel cobalt Compound is the oxide that Formulas I compound represented or Formulas I compound represented are obtained through peroxidating：

Ni1-x-yCoxMy(OH)2Formulas I,

In Formulas I, 0.05≤x≤0.30,0.01≤y≤0.20,

M is one or more of Mn, Al, Ti, Mg, Zr, Ca, Zn, Sr, La and B；

Doped chemical in the doped compound is Al, Ti, Mg, Zr, Ca, Zn, B, F, V, Sr, Ba, Y, Nd, Cs, W, One or more of Mo, Ru, Rd and lanthanide series；

The molal quantity and the ratio of the molal quantity of Li that the compound of the nickel cobalt and the dosage of lithium compound make Ni, Co and M total It is worth for 1:(0.9~1.15)；

Will described matrix and covering mix after it is dry, obtain cladding product, the cladding element in the covering includes One or more of magnesium, titanium, zirconium, fluorine, boron, aluminium and phosphate radical；

The cladding product is calcined, obtains nickelic positive electrode.

Preferably, after obtaining matrix, further include：

Described matrix and detergent are mixed, obtain mixture；

It is dry after the mixture and covering are mixed, obtain cladding product.

Preferably, the doped compound is one or more of oxide, carbonate and nitrate of doped chemical.

Preferably, described matrix and the temperature of detergent mixing are 0 DEG C~80 DEG C.

Preferably, the detergent includes one or more of water, ethyl alcohol, propyl alcohol, isopropanol and acetone.

Preferably, the covering is nitrate, sulfate or the chlorate of cladding element.

The preparation method of nickelic positive electrode provided by the invention is by preparing the base material containing doped chemical, and to base material It is coated, lithium ion battery prepared by the nickelic positive electrode that the present invention is prepared by element doping has preferable Capacity and cycle performance.In addition, method provided by the invention makes the nickelic positive electrode being prepared have preferably by cladding Electrochemical stability and security.

Description of the drawings

It in order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this The embodiment of invention, for those of ordinary skill in the art, without creative efforts, can also basis The attached drawing of offer obtains other attached drawings.

Fig. 1 is the nickelic positive electrode SEM figures that comparative example 1 of the present invention is prepared；

Fig. 2 is the nickelic positive electrode SEM figures that comparative example 2 of the present invention is prepared；

Fig. 3 is the nickelic positive electrode SEM figures that the embodiment of the present invention 1 is prepared；

Fig. 4 is the button cell 1C charge and discharges for the nickelic positive electrode that comparative example 1~2 of the present invention and embodiment 1 are prepared Electric circulation volume conservation rate curve.

Specific embodiment

Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, those of ordinary skill in the art are obtained every other without making creative work Embodiment belongs to the scope of protection of the invention.

The present invention provides a kind of nickelic positive electrode, including：

Matrix, the preparation method of described matrix are：

It is calcined after the compound of nickel cobalt, lithium compound and doping element compound are mixed, obtains matrix, the nickel cobalt It is the oxide that Formulas I compound represented or Formulas I compound represented are obtained through peroxidating to close object：

Ni1-x-yCoxMy(OH)2Formulas I,

In Formulas I, 0.05≤x≤0.30,0.01≤y≤0.20, in M Mn, Al, Ti, Mg, Zr, Ca, Zn, Sr, La and B One or more；

Doped chemical in the doping element compound is Al, Ti, Mg, Zr, Ca, Zn, B, F, V, Sr, Ba, Y, Nd, One or more of Cs, W, Mo, Ru, Rd and lanthanide series；

The molal quantity and the ratio of the molal quantity of Li that the nickel cobalt compound and the dosage of lithium compound make Ni, Co and M total For 1:(0.9~1.15)；

The clad on described matrix surface is coated on, contains magnesium, titanium, zirconium, fluorine, boron, aluminium and phosphate radical in the clad One or more of.

Nickelic positive electrode provided by the invention includes matrix, and the preparation method of described matrix is：By the compound of nickel cobalt, It is calcined after lithium compound and doping element compound mixing, obtains matrix.In an embodiment of the present invention, the chemical combination of the nickel cobalt The temperature calcined after object, lithium compound and doping element compound mixing is 600 DEG C~900 DEG C；In other examples, institute It is 700 DEG C~800 DEG C to state the temperature calcined after compound, lithium compound and the doping element compound mixing of nickel cobalt；In addition Embodiment in, the temperature calcined after the compound of the nickel cobalt, lithium compound and doping element compound mixing for 740 DEG C~ 760℃.In an embodiment of the present invention, calcined after the compound of the nickel cobalt, lithium compound and doping element compound mixing Time for 5 it is small when~40 it is small when；In other examples, the compound of the nickel cobalt, lithium compound and doped chemical Close after object mixing time for calcining for 10 it is small when~30 it is small when；In a further embodiment, the compound of the nickel cobalt, lithiumation are closed After object and doping element compound mixing time for calcining for 15 it is small when~25 it is small when.In an embodiment of the present invention, Ke Yi Under conditions of air or oxygen, calcined after the compound of nickel cobalt, lithium compound and doping element compound are mixed.

In an embodiment of the present invention, forged after the compound of the nickel cobalt, lithium compound and doping element compound mixing After the completion of burning, the calcined product crushing and screening that will obtain obtains matrix.In an embodiment of the present invention, the crushing and screening Granularity is 3 microns~20 microns；In other examples, the granularity of the crushing and screening is 5 microns~15 microns；In addition Embodiment in, the granularity of the crushing and screening is 8 microns~12 microns.

In the present invention, the compound of the nickel cobalt is Formulas I compound represented or Formulas I compound represented through peroxidating Obtained oxide.In an embodiment of the present invention, in the Formulas I, x is 0.1~0.25；In other examples, the x For 0.15~0.2.In an embodiment of the present invention, in the Formulas I, y is 0.05~0.15；In other examples, the y For 0.08~0.12.In an embodiment of the present invention, the preparation method of the nickel cobalt compound is：

Under the action of ammonium hydroxide and sodium hydroxide, nickel salt solution, cobalt salt solution and M salting liquids are subjected to coprecipitation reaction, Formulas I compound represented is obtained, the M is one or more of Mn, Al, Ti, Mg, Zr, Ca, Zn, Sr, La and B.

In an embodiment of the present invention, nickel salt solution, cobalt salt solution and M salting liquids can be mixed, obtains mixed solution； Ammonia spirit, sodium hydroxide solution and the mixed solution cocurrent are added in and carry out coprecipitation reaction, obtains the chemical combination shown in Formulas I Object.

In an embodiment of the present invention, the temperature of the coprecipitation reaction is 35 DEG C~70 DEG C；In other examples, The temperature of the coprecipitation reaction is 40 DEG C~60 DEG C；In a further embodiment, the temperature of the coprecipitation reaction is 45 DEG C ~55 DEG C.In an embodiment of the present invention, coprecipitation reaction can be carried out under conditions of stirring.In the embodiment of the present invention In, after the completion of the coprecipitation reaction, obtained reaction product is washed, is dried, obtain Formulas I compound represented. In the embodiment of the present invention, the drying temperature of the reaction product is 90 DEG C~110 DEG C；In other examples, it is described anti- The drying temperature for answering product is 100 DEG C.

In an embodiment of the present invention, the ammonium hydroxide is ammonia spirit.In an embodiment of the present invention, the ammonia spirit Mass concentration be 15%~28%；In other examples, the percentage composition of the ammonia spirit is 20%~25%. In the embodiment of the present invention, the dosage of the ammonium hydroxide is 2L~8L.In an embodiment of the present invention, the sodium hydroxide is hydrogen-oxygen Change sodium solution.In an embodiment of the present invention, the molar concentration of the sodium hydroxide solution is 2mol/L~4mol/L；At other Embodiment in, the molar concentration of the sodium hydroxide solution is 2.5mol/L~3.5mol/L；In a further embodiment, institute The molar concentration for stating sodium hydroxide solution is 3mol/L.In an embodiment of the present invention, the dosage of the sodium hydroxide for 5L~ 15L。

In an embodiment of the present invention, the nickel salt is nickel sulfate, nickel nitrate or nickel chloride.In the embodiment of the present invention In, the cobalt salt is cobaltous sulfate, cobalt nitrate or cobalt chloride.In an embodiment of the present invention, the M salt is the nitrate of M, chlorination Salt, sulfate or oxalates；In other examples, the M salt is aluminum nitrate, aluminium chloride, manganese sulfate, manganese chloride or oxalic acid Manganese.In an embodiment of the present invention, the dosage of the nickel salt solution, cobalt salt solution and M salting liquids makes the molar ratio of nickel, cobalt and M For (0.5~0.94):(0.05~0.3):(0.01~0.2).In an embodiment of the present invention, the nickel salt solution, cobalt salt are molten The concentration that metal ion total in mixed solution is obtained after liquid and the mixing of M salting liquids is 2mol/L~3mol/L；Other real It applies in example, the concentration that metal ion total in mixed solution is obtained after the nickel salt solution, cobalt salt solution and the mixing of M salting liquids is 2.2mol/L~2.8mol/L；In a further embodiment, obtained after the nickel salt solution, cobalt salt solution and the mixing of M salting liquids The concentration of total metal ion is 2.4mol/L~2.6mol/L in mixed solution.

In an embodiment of the present invention, the Formulas I compound represented is aoxidized, obtained oxide also can conduct Nickel cobalt compound.In an embodiment of the present invention, the temperature of the oxidation is 380 DEG C~420 DEG C；In other examples, The temperature of the oxidation is 400 DEG C.In an embodiment of the present invention, the time of the oxidation for 12 it is small when~16 it is small when；At it In his embodiment, time of the oxidation for 14 it is small when~15 it is small when.In an embodiment of the present invention, the atmosphere of the oxidation For air.

In an embodiment of the present invention, the lithium compound is included in lithium carbonate, lithium hydroxide, lithium nitrate and lithium oxalate It is one or more of；In other examples, the lithium compound is lithium carbonate, lithium hydroxide, lithium nitrate or lithium oxalate.

In the present invention, the doped chemical in the doping element compound for Al, Ti, Mg, Zr, Ca, Zn, B, F, V, One or more of Sr, Ba, Y, Nd, Cs, W, Mo, Ru, Rd and lanthanide series.In an embodiment of the present invention, the doping Element is Al, Ti, Mg, Zr, Ca, Zn, B, F, V, Sr, Ba, Y, Nd, Cs, W, Mo, Ru, Rd or lanthanide series.In the reality of the present invention It applies in example, the doping element compound is one or more of oxide, carbonate and nitrate of doped chemical；At it In his embodiment, the doping element compound is lanthanum nitrate, magnesium nitrate or titanium oxide.

In the present invention, the nickel cobalt compound and the dosage of lithium compound make Ni, Co and M total molal quantity and Li's rubs The ratio of your number is 1:(0.9~1.15)；In an embodiment of the present invention, the nickel cobalt compound and the dosage of lithium compound make Ni, Co and M total molal quantity and the ratio of the molal quantity of Li are 1:(0.98~1.12).In an embodiment of the present invention, it is described The quality of doping element compound is the 0.5%~1% of the compound quality of nickel cobalt；In other examples, the doping The quality of element compound is the 0.6%~0.9% of the compound quality of nickel cobalt；In a further embodiment, the doping member The quality of plain compound is the 0.7%~0.8% of the compound quality of nickel cobalt.In an embodiment of the present invention, the doping member The dosage of plain compound makes the quality of doped chemical in described matrix for Ni, Co and the A% of M element gross mass, 0 ＜ A≤3.

Nickelic positive electrode provided by the invention is coated on the clad on described matrix surface, contains in the clad There are one or more of magnesium, titanium, zirconium, fluorine, boron, aluminium and phosphate radical.In an embodiment of the present invention, contain in the clad Magnesium, titanium, zirconium, fluorine, boron or aluminium.In an embodiment of the present invention, the quality of the clad is the B%, 0 ＜ of described matrix quality B≤5；In other examples, the quality of the clad is the 0.5%~4% of described matrix quality；In other implementation In example, the quality of the clad is the 1%~3% of described matrix quality.

A kind of preparation method of nickelic positive electrode described in the present invention provides above-mentioned technical proposal, including：

It is calcined after the compound of nickel cobalt, lithium compound and doping element compound are mixed, obtains matrix, the nickel cobalt Compound is the oxide that Formulas I compound represented or Formulas I compound represented are obtained through peroxidating：

Ni1-x-yCoxMy(OH)2Formulas I,

In Formulas I, 0.05≤x≤0.30,0.01≤y≤0.20,

M is one or more of Mn, Al, Ti, Mg, Zr, Ca, Zn, Sr, La and B；

Doped chemical in the doping element compound is Al, Ti, Mg, Zr, Ca, Zn, B, F, V, Sr, Ba, Y, Nd, One or more of Cs, W, Mo, Ru, Rd and lanthanide series；

The molal quantity and the ratio of the molal quantity of Li that the compound of the nickel cobalt and the dosage of lithium compound make Ni, Co and M total It is worth for 1:(0.9~1.15)；

Will described matrix and covering mix after it is dry, obtain cladding product, the cladding element in the covering includes One or more of magnesium, titanium, zirconium, fluorine, boron, aluminium and phosphate radical；

The cladding product is calcined, obtains nickelic positive electrode.

In the present invention, the preparation method of described matrix is consistent with the preparation method of matrix described in above-mentioned technical proposal, Details are not described herein.

After obtaining matrix, the present invention is dry after mixing described matrix and covering, obtains cladding product.The present invention's In embodiment, drying after covering can be added dropwise into described matrix, obtain cladding product.In an embodiment of the present invention, institute Dry temperature is stated as 80 DEG C~150 DEG C；In other examples, the temperature of the drying is 90 DEG C~140 DEG C；In addition Embodiment in, the temperature of the drying is 100 DEG C~130 DEG C.In an embodiment of the present invention, the method for the drying is baking It is dry.In an embodiment of the present invention, filter after the mixture and covering being mixed and be dried again, obtain cladding production Object.

After obtaining matrix, in an embodiment of the present invention, described matrix and detergent can be mixed, obtain mixture； It is dry after the mixture and covering are mixed, obtain cladding product.In the present invention, matrix and detergent are mixed to base Body is washed, and can reduce the impurity lithium content on the nickelic positive electrode surface that the present invention is prepared, and further improves this Invent the capacity and cycle performance of lithium ion battery prepared by the nickelic positive electrode being prepared.In the embodiment of the present invention In, the temperature of described matrix and detergent mixing is 0 DEG C~80 DEG C；In other examples, described matrix and detergent mix The temperature of conjunction is 20 DEG C~60 DEG C；In a further embodiment, described matrix and the temperature of detergent mixing are 30 DEG C~50 DEG C. In an embodiment of the present invention, described matrix and detergent can be mixed under conditions of stirring.In the embodiment of the present invention In, time >=5 minute of the stirring.

In an embodiment of the present invention, the detergent include water, ethyl alcohol, propyl alcohol, isopropanol and acetone in one kind or It is several；In other examples, the detergent is water, ethyl alcohol, propyl alcohol, isopropanol or acetone.In the embodiment of the present invention In, the water is deionized water.

In the present invention, by base described in dry method and above-mentioned technical proposal after the mixture and covering being mixed Body method dry after being mixed with covering is consistent, and details are not described herein.

In the present invention, the cladding element in the covering includes one in magnesium, titanium, zirconium, fluorine, boron, aluminium and phosphate radical Kind is several.In an embodiment of the present invention, the covering is nitrate, sulfate or the chlorate of cladding element；At it In his embodiment, the covering is nitrate or sulfate, the nitrate of zirconium or sulfate, the nitrate or sulphur of aluminium of magnesium The nitrate or chlorate of hydrochlorate, calcium.In an embodiment of the present invention, the dosage of the covering is described in above-mentioned technical proposal The B% of mixture quality, 0 ＜ B≤5.

After obtaining cladding product, the present invention calcines the cladding product, obtains nickelic positive electrode.In the present invention Embodiment in, it is described cladding product calcining heat be 300 DEG C~800 DEG C；In other examples, the cladding product Calcining heat be 400 DEG C~700 DEG C；In a further embodiment, the calcining heat of the cladding product is 500 DEG C~600 ℃.In an embodiment of the present invention, it is described cladding product calcination time for 2 it is small when~20 it is small when；In other examples, It is described cladding product calcination time for 5 it is small when~15 it is small when；In a further embodiment, the calcination time of the cladding product For 8 it is small when~12 it is small when.In an embodiment of the present invention, can under conditions of air or oxygen, by it is described cladding product into Row calcining.In an embodiment of the present invention, after the completion of the cladding product calcining, will be sieved after obtained calcined product furnace cooling Point, obtain nickelic positive electrode.

The present invention provides a kind of lithium ion battery, the positive electrode of the lithium ion battery is described in above-mentioned technical proposal Nickelic positive electrode or above-mentioned technical proposal described in the nickelic positive electrode that is prepared of method.In the present invention, it is described Doped chemical is contained on nickelic positive electrode surface, has the lithium ion battery that this nickelic positive electrode is prepared preferable Capacity and cycle performance.

The present invention does not have the preparation method of the lithium ion battery special limitation, using known to those skilled in the art The technical solution that positive electrode is prepared into lithium ion battery, pour lithium slice such as can be used as auxiliary electrode, this is sent out The nickelic positive electrode of bright offer is assembled into button cell, and specific method is：

Nickelic positive electrode provided by the invention, acetylene black, Kynoar and N-Methyl pyrrolidone are mixed, obtained Anode sizing agent；

It is dry after the anode sizing agent is coated on aluminium foil, obtain positive plate；

Using pour lithium slice as negative plate；

Positive plate, electrolyte, membrane and negative plate are assembled, obtain button cell.

In an embodiment of the present invention, the mass ratio of the nickelic positive electrode, acetylene black and Kynoar (PVDF) For (88~92):(4~6):(4~6)；In other examples, the quality of the nickelic positive electrode, acetylene black and PVDF Than for 90:5:5.In an embodiment of the present invention, can under conditions of stirring by nickelic positive electrode, acetylene black, PVDF and NMP is mixed.

In an embodiment of the present invention, it is 75 DEG C~85 DEG C anode sizing agent to be coated on temperature dry on aluminium foil；At it In his embodiment, it is 80 DEG C that anode sizing agent is coated on temperature dry on aluminium foil.In an embodiment of the present invention, can incite somebody to action It is cut after dried positive plate tabletting.In an embodiment of the present invention, the positive plate can be circular positive plate.In this hair In bright embodiment, the diameter of the positive plate can be 13mm~15mm；In other examples, the positive plate is straight Footpath can be 14mm.In an embodiment of the present invention, the negative plate can be circular negative plate.In the embodiment of the present invention In, the diameter of the negative plate can be 15mm~17mm；In other examples, the diameter of the negative plate can be 16mm。

In an embodiment of the present invention, the electrolyte is LiPF6Solution, the LiPF6The solvent of solution is ethylene carbonate Ester (EC) and dimethyl carbonate (DMC), the LiPF6The concentration of solution is 1mol/L.In an embodiment of the present invention, it is described every Film is poly- Celgard propylene microcellulars film.In an embodiment of the present invention, battery pack can be carried out in the glove box full of argon gas Dress.

The PHB-4 types pH meter provided using Shanghai precision instrumentation company tests nickelic positive electrode provided by the invention PH value, test result is, the pH value of nickelic positive electrode provided by the invention is ＜ 11.5.

The surface impurity lithium content of nickelic positive electrode provided by the invention is tested using the method for acid base titration, under It states formula and calculates impurity lithium content：

Impurity lithium content=6.941 × (Li2CO3The ÷ 73.886+LiOH% ÷ 23.941 of % × 2)

Test result is that nickelic positive electrode surface impurity lithium content provided by the invention is ＜ 0.083%.

Nickelic positive electrode provided by the invention is prepared into button cell by the following method, is specially：

Positive electrode provided by the invention, acetylene black and PVDF are pressed 90:5:5 mass ratioes weigh, and are uniformly mixed, and add in NMP stirs 2h, obtains anode sizing agent；80 DEG C of vacuum bakeouts after the anode sizing agent is uniformly coated on aluminium foil, tabletting are cut out It cuts, obtains the positive plate of a diameter of 14mm；

Using the pour lithium slice of a diameter of 16mm as negative plate；

By above-mentioned positive plate, negative plate, with 1mol/L LiPF6+ DEC/EC (volume ratios 1:1) mixed solution is electrolyte, Using poly- Celgard propylene microcellulars film as membrane, assembled in the glove box full of argon gas, obtain button cell.

Using LAND battery test systems (CT2001A), in the voltage range of 3.0~4.3V, 25 DEG C, 0.1C charge and discharge Under the conditions of, test above-mentioned button cell first discharge specific capacity；Test result is prepared by nickelic positive electrode provided by the invention 25 DEG C of button cell, first discharge specific capacity is 194mAh/g~204mAh/g under the conditions of 0.1C.

Using LAND battery test systems (CT2001A), test 50 weeks capacity of above-mentioned button cell 1C charge and discharge cycles and protect Holdup；Test result is that 50 weeks capacity of button cell 1C charge and discharge cycles prepared by nickelic positive electrode provided by the invention are protected Holdup ＞ 96%.

Raw material used in following embodiment of the present invention is commercial goods.

Comparative example 1

Nickel sulfate solution, cobalt sulfate solution and aluminum nitrate solution are uniformly mixed, obtain mixed solution, the sulfuric acid is molten The dosage of liquid, cobalt sulfate solution and aluminum nitrate solution makes the molar ratio of nickel, cobalt and aluminium be 0.8:0.15:0.05, the mixing is molten Total concentration of metal ions is 2.5mol/L in liquid；

Ammonia spirit, the NaOH solution of 3mol/L and the mixed solution cocurrent that mass percentage is 20% are added in In reaction kettle, the addition speed of the mixed solution is 12mL/min, and the addition speed of ammonia spirit is 1mL/min, and NaOH is molten The addition speed of liquid is 5ml/L, and heating stirring carries out precipitation reaction at 35 DEG C, 100 after obtained reaction product is washed DEG C drying, obtain Ni0.8Co0.15Al0.05(OH)2Compound；

By above-mentioned Ni0.8Co0.15Al0.05(OH)2Compound carried out at air atmosphere, 400 DEG C 15 it is small when oxidation processes After sieve, obtain nickel cobalt aluminium compound；

Nickel cobalt aluminium compound obtained above is uniformly mixed into 1.5h with lithium hydroxide, lanthanum nitrate, the nickel cobalt calorize is closed The molal quantity and the ratio of the molal quantity of Li that object and lithium hydroxide dosage make Ni, Co and Al total are 1：1.06, the addition of lanthanum nitrate It measures as the 0.5% of above-mentioned nickel cobalt aluminium compound quality, after mixture obtained above is calcined 15h at oxygen atmosphere, 800 DEG C Crushing and screening obtains doped products；

Above-mentioned doped products are calcined into 6h for 650 DEG C under air atmosphere, obtain nickelic positive electrode.

SEM detections are carried out to the nickelic positive electrode that comparative example 1 of the present invention is prepared, testing result is as shown in Figure 1, figure The 1 nickelic positive electrode SEM figures being prepared for comparative example 1 of the present invention.

According to the method described in above-mentioned technical proposal, the nickelic positive electrode that comparative example 1 of the present invention is prepared is tested PH value, test result are that the pH value for the nickelic positive electrode that comparative example 1 of the present invention is prepared is 11.92.

According to the method described in above-mentioned technical proposal, the nickelic positive electrode table that comparative example 1 of the present invention is prepared is tested Face impurity lithium content, the first discharge specific capacity and capacity retention ratio of the button cell of preparation；Test result such as table 1 and Fig. 4 institutes Show, the performance test results for the nickelic positive electrode that table 1 is prepared for the embodiment of the present invention and comparative example, Fig. 4 is the present invention The button cell 1C charge and discharge cycles capacity retention ratio for the nickelic positive electrode that comparative example 1~2 and embodiment 1 are prepared is bent Line.

Comparative example 2

Nickel cobalt aluminium compound is prepared according to the method described in comparative example 1 of the present invention；

Nickel cobalt aluminium compound obtained above is uniformly mixed into 1.5h, the nickel cobalt aluminium compound and hydrogen-oxygen with lithium hydroxide The molal quantity and the ratio of the molal quantity of Li that change lithium dosage makes Ni, Co and Al total are 1：1.06, mixture obtained above is existed Oxygen atmosphere calcines crushing and screening after 15h at 800 DEG C, obtains intermediate product；

After above-mentioned intermediate product is stirred 0.5h in 60 DEG C of deionized water, it is 130g/L that mass concentration is added dropwise thereto Aluminum nitrate solution, the quality of the deionized water is 1.5 times of above-mentioned intermediate product quality, and the quality of the aluminum nitrate is upper The 1% of intermediate product quality is stated, is dried after obtained mixture is filtered at 100 DEG C, obtains cladding product；

Above-mentioned cladding product is calcined into 6h for 650 DEG C under air atmosphere, obtains nickelic positive electrode.

SEM detections are carried out to the nickelic positive electrode that comparative example 2 of the present invention is prepared, testing result is as shown in Fig. 2, figure The 2 nickelic positive electrode SEM figures being prepared for comparative example 2 of the present invention.

According to the method described in above-mentioned technical proposal, the nickelic positive electrode that comparative example 2 of the present invention is prepared is tested PH value, test result are that the pH value for the nickelic positive electrode that comparative example 2 of the present invention is prepared is 11.4.

According to the method described in above-mentioned technical proposal, the nickelic positive electrode table that comparative example 2 of the present invention is prepared is tested Face impurity lithium content, the first discharge specific capacity and capacity retention ratio of the button cell of preparation；Test result such as table 1 and Fig. 4 institutes Show.

Embodiment 1

Nickel cobalt aluminium compound is prepared according to the method described in comparative example 1 of the present invention；

Nickel cobalt aluminium compound obtained above is uniformly mixed into 1.5h with lithium hydroxide, lanthanum nitrate, the nickel cobalt calorize is closed The molal quantity and the ratio of the molal quantity of Li that object and lithium hydroxide dosage make Ni, Co and Al total are 1：1.06, the addition of lanthanum nitrate It measures as the 0.5% of above-mentioned nickel cobalt aluminium compound quality, after mixture obtained above is calcined 15h at oxygen atmosphere, 800 DEG C Crushing and screening obtains doped products；

After above-mentioned doped products are stirred 0.5h in 60 DEG C of deionized water, it is 130g/L that mass concentration is added dropwise thereto Aluminum nitrate solution, the quality of the deionized water is 1.5 times of above-mentioned doped products quality, and the quality of the aluminum nitrate is upper The 1% of doped products quality is stated, is dried after obtained mixture is filtered at 100 DEG C, obtains cladding product；

Above-mentioned cladding product is calcined into 6h for 650 DEG C under air atmosphere, obtains nickelic positive electrode.

SEM detections are carried out to the nickelic positive electrode that the embodiment of the present invention 1 is prepared, testing result is as shown in figure 3, figure The 3 nickelic positive electrode SEM figures being prepared for the embodiment of the present invention 1.

According to the method described in above-mentioned technical proposal, the nickelic positive electrode that the embodiment of the present invention 1 is prepared is tested PH value, test result are that the pH value for the nickelic positive electrode that the embodiment of the present invention 1 is prepared is 11.32.

According to the method described in above-mentioned technical proposal, the nickelic positive electrode table that the embodiment of the present invention 1 is prepared is tested Face impurity lithium content, the first discharge specific capacity and capacity retention ratio of the button cell of preparation；Test result such as table 1 and Fig. 4 institutes Show.

Embodiment 2

Nickel sulfate solution, cobalt sulfate solution and manganese chloride solution are uniformly mixed, obtain mixed solution, the nickel sulfate is molten The dosage of liquid, cobalt sulfate solution and manganese chloride solution makes the molar ratio of nickel, cobalt and manganese be 0.8:0.1:0.1, the mixed solution In total concentration of metal ions be 3mol/L；

By ammonia spirit that mass percentage is 15%, concentration be 3mol/L NaOH solution and the mixed solution simultaneously Stream is added in reaction kettle, and the addition speed of the mixed solution is 15mL/min, and the addition speed of ammonia spirit is 2mL/min, The addition speed of NaOH solution is 4mL/min, and heating stirring carries out precipitation reaction at 50 DEG C, and obtained reaction product is washed Afterwards in 100 DEG C of drying, Ni is obtained0.8Co0.1Mn0.1(OH)2Nickel cobalt manganese compound；

Nickel cobalt manganese compound obtained above is uniformly mixed into 2.5h, the nickel cobalt manganese chemical combination with lithium hydroxide, magnesium nitrate The molal quantity and the ratio of the molal quantity of Li that object and lithium hydroxide dosage make Ni, Co and Al total are 1：1.05, the addition of magnesium nitrate It measures as the 1% of above-mentioned nickel cobalt manganese compound quality, is broken after mixture obtained above is calcined 10h at oxygen atmosphere, 700 DEG C Broken screening, obtains doped products；

After above-mentioned doped products are stirred 1h in 25 DEG C of deionized water, it is 100g/L's that mass concentration is added dropwise thereto Calcium nitrate solution, the quality of the deionized water are 1.5 times of above-mentioned doped products quality, and the quality of the calcium nitrate is above-mentioned The 1.5% of doped products quality is dried after obtained mixture is filtered at 120 DEG C, obtains cladding product；

Above-mentioned cladding product is calcined into 10h for 400 DEG C under air atmosphere, obtains nickelic positive electrode.

According to the method described in above-mentioned technical proposal, the nickelic positive electrode that the embodiment of the present invention 2 is prepared is tested PH value, test result are that the pH value for the nickelic positive electrode that the embodiment of the present invention 2 is prepared is 11.26.

According to the method described in above-mentioned technical proposal, the nickelic positive electrode table that the embodiment of the present invention 2 is prepared is tested Face impurity lithium content, the first discharge specific capacity and capacity retention ratio of the button cell of preparation；Test result is as shown in table 1.

Embodiment 3

Nickel nitrate solution, cobalt chloride cobalt liquor and manganese chloride solution are uniformly mixed, obtain mixed solution, the nickel nitrate The dosage of solution, cobalt chloride solution and manganese chloride solution makes the molar ratio of nickel, cobalt and manganese be 0.9:0.05:0.05, the mixing Total concentration of metal ions is 2.5mol/L in solution；

By ammonia spirit that mass percentage is 18%, concentration be 3mol/L NaOH solution and the mixed solution simultaneously Stream is added in reaction kettle, and the addition speed of the mixed solution is 12mL/min, and the addition speed of ammonia spirit is 1.5mL/ Min, the addition speed of NaOH solution is 4mL/min, and heating stirring carries out precipitation reaction, the reaction product that will be obtained at 45 DEG C It is dried after washing at 100 DEG C, obtains Ni0.9Co0.05Mn0.05(OH)2Nickel cobalt manganese compound；

Nickel cobalt manganese compound obtained above is uniformly mixed into 2h, the nickel cobalt manganese compound with lithium hydroxide, titanium oxide The molal quantity and the ratio of the molal quantity of Li for making Ni, Co and Al total with lithium hydroxide dosage are 1：1.07, the addition of titanium oxide For the 0.5% of above-mentioned nickel cobalt manganese compound quality, broken after mixture obtained above is calcined 15h at oxygen atmosphere, 780 DEG C Broken screening, obtains doped products；

After above-mentioned doped products are stirred 0.5h in 0 DEG C of deionized water, it is 150g/L that mass concentration is added dropwise thereto Calcium chloride solution, the quality of the deionized water is 1.5 times of above-mentioned doped products quality, and the quality of the calcium chloride is upper The 0.4% of doped products quality is stated, is dried after obtained mixture is filtered at 80 DEG C, obtains cladding product；

Above-mentioned cladding product is calcined into 12h for 600 DEG C under air atmosphere, obtains nickelic positive electrode.

According to the method described in above-mentioned technical proposal, the nickelic positive electrode that the embodiment of the present invention 3 is prepared is tested PH value, test result are that the pH value for the nickelic positive electrode that the embodiment of the present invention 3 is prepared is 11.32.

According to the method described in above-mentioned technical proposal, the nickelic positive electrode table that the embodiment of the present invention 3 is prepared is tested Face impurity lithium content, the first discharge specific capacity and capacity retention ratio of the button cell of preparation；Test result is as shown in table 1.

The performance test results for the nickelic positive electrode that 1 embodiment of the present invention of table and comparative example are prepared

Remaining total impurities lithium % Discharge capacity mAh/g Capacity retention ratio % Comparative example 1 0.2630% 193.2 96.4% Comparative example 2 0.0844% 192.4 90.5% Embodiment 1 0.0739% 194.4 96.6% Embodiment 2 0.0713% 194.9 96.3% Embodiment 3 0.0821% 204.8 96.8%

As seen from the above embodiment, the present invention provides a kind of nickelic positive electrode, including：Matrix, described matrix surface Doped with Al, Ti, Mg, Zr, Ca, Zn, B, F, V, Sr, Ba, Y, Nd, Cs, W, Mo, Ru, Rd or lanthanide series；It is coated on the base The clad in body surface face contains one or more of magnesium, titanium, zirconium, fluorine, boron, aluminium and phosphate radical in the clad.The present invention The nickelic positive electrode matrix surface provided contains doped chemical, the element of doping can stabilized matrix surface crystal structure, delay Cleaning solution is solved to substrate material surface structural damage, the capacity of lithium ion battery and cycle performance for preparing nickelic positive electrode Preferably.In addition, this nickelic positive electrode carries clad, clad can be such that positive electrode isolates with anolyte portion, carry The electrochemical stability and security of high positive electrode.

Claims (2)

1. a kind of preparation method of nickelic positive electrode is specially：
Nickel nitrate solution, cobalt chloride solution and manganese chloride solution are uniformly mixed, obtain mixed solution, the nickel nitrate solution, The dosage of cobalt chloride solution and manganese chloride solution makes the molar ratio of nickel, cobalt and manganese be 0.9:0.05:0.05, in the mixed solution Total concentration of metal ions is 2.5mol/L；
NaOH solution that ammonia spirit that mass percentage is 18%, concentration are 3mol/L and the mixed solution cocurrent are added Entering in reaction kettle, the addition speed of the mixed solution is 12mL/min, and the addition speed of ammonia spirit is 1.5mL/min, The addition speed of NaOH solution is 4mL/min, and heating stirring carries out precipitation reaction at 45 DEG C, and obtained reaction product is washed It is dried afterwards at 100 DEG C, obtains Ni0.9Co0.05Mn0.05(OH)2Nickel cobalt manganese compound；
Obtained nickel cobalt manganese compound is uniformly mixed into 2h, the nickel cobalt manganese compound and hydroxide with lithium hydroxide, titanium oxide The molal quantity and the ratio of the molal quantity of Li that lithium dosage makes Ni, Co and Mn total are 1：1.07, the addition of titanium oxide is above-mentioned nickel Mixture obtained above is calcined at oxygen atmosphere, 780 DEG C crushing and screening after 15h by the 0.5% of Co-Mn compound quality, Obtain doped products；
After above-mentioned doped products are stirred 0.5h in 0 DEG C of deionized water, the chlorine that mass concentration is 150g/L is added dropwise thereto Change calcium solution, the quality of the deionized water is 1.5 times of above-mentioned doped products quality, and the quality of the calcium chloride is mixed to be above-mentioned The 0.4% of miscellaneous product quality is dried after obtained mixture is filtered at 80 DEG C, obtains cladding product；
Above-mentioned cladding product is calcined into 12h for 600 DEG C under air atmosphere, obtains nickelic positive electrode.
2. a kind of lithium ion battery, the positive electrode method described in claim 1 of the lithium ion battery is prepared Nickelic positive electrode.
CN201510545968.7A 2015-08-31 2015-08-31 A kind of nickelic positive electrode and preparation method thereof and lithium ion battery CN105070907B (en)

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