CN108365216A - The novel nickelic tertiary cathode material of one kind and preparation - Google Patents

The novel nickelic tertiary cathode material of one kind and preparation Download PDF

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Publication number
CN108365216A
CN108365216A CN201810349653.9A CN201810349653A CN108365216A CN 108365216 A CN108365216 A CN 108365216A CN 201810349653 A CN201810349653 A CN 201810349653A CN 108365216 A CN108365216 A CN 108365216A
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cathode material
tertiary cathode
novel
nickelic tertiary
reaction
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李星
张康家
王明珊
刘杨
蒋飞
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Southwest Petroleum University
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Southwest Petroleum University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention relates to a kind of novel nickelic tertiary cathode material and preparations, belong to field of lithium ion battery anode.The present invention prepares Ni by coprecipitation firstxCoyMnz(OH)2(x+y+z=1,y≦0.1,0.6<x<0.8) spherical precursor, is then mixed by Rheological Phase Method with stoichiometric ratio lithium salts, and ball-type LiNi is prepared using high-temperature calcinationxCoyMnzO2(x+y+z=1,y≦0.1,0.6<x<0.8) nickelic tertiary cathode material.Since the content control of Ni is controlled 0.1 in the content of 0.6 ~ 0.8, Co hereinafter, therefore ensure that high power capacity, inexpensive characteristic.In addition, by adjusting the stoichiometric ratio of Ni and Mn, cationic mixing degree, stabilizing material surface crystal structure can also be reduced.Above-mentioned nickelic tertiary cathode material tap density ~ 3.5mg/cm3, reversible capacity is up to 200mAh/g, has excellent cycle performance and high rate performance, has broad application prospects as lithium ion battery with high energy density positive electrode.

Description

The novel nickelic tertiary cathode material of one kind and preparation
Technical field
The present invention relates to field of lithium ion battery anode, especially a kind of novel nickelic tertiary cathode material and its system Preparation Method.
Background technology
Positive electrode is one of core material of lithium ion battery, the fine or not electricity to lithium ion battery of positive electrode performance Chemical property plays the role of conclusive.Therefore, particularly necessary for the research and development of positive electrode, search out that capacity is big, cycle Stability is good, safe and positive electrode at low cost always is the target of researchers.LiCoO at present2Positive electrode Business degree highest, production technology are also the most ripe, and a large amount of share is occupied in the market in current positive electrode.However, LiCoO2Material itself haves the shortcomings that some are notable:First, Co are to belong to rare element, are not easy to exploit, and improve the material The production cost of material;Second, Co are toxic, and certain injury can be all caused to human body and environment;Third, LiCoO2Actual discharge ratio Capacity is low, only the half or so of theoretical capacity;4th, the stability of the material in use is poor, is easy to bring peace Full hidden danger, these defects limit the material, and share further expands in the market.
Lithium nickelate(LiNiO2)The specific capacity of positive electrode is larger, but the production of non-stoichiometric can be generated when preparation Object, results in structural stability and thermal stability is poor.LiMn of the LiMn2O4 in addition to spinel structure2O4Outside, also layer structure LiMnO2.Its laminate LiMnO2Specific capacity is bigger, but it belongs to thermodynamic (al) metastable state, structural instability, there is Jahn-Teller effects and cause cycle performance poor, and chemical property decaying is fast, the LiMn of spinel structure2O4Technique Simply, cheap, charging/discharging voltage is high, and environmentally friendly, security performance is excellent, but specific capacity is relatively low, and capacity declines under high temperature Subtract more serious.LiFePO4 belongs to newer positive electrode, and the safe of it, cost are relatively low, but that there is discharge voltages is low (3.4V), the shortcomings of tap density is low, poorly conductive, and batch production is difficult.The shortcomings that above-mentioned several positive electrodes, all constrains The further development and application of itself, therefore find novel anode material for lithium-ion batteries and become the emphasis of research.
LiCoO2, LiNiO2It is all α-NaFeO2Structure, and Ni, Co, Mn are with period adjacent element, and this means that them It can be mixed to form solid solution with arbitrary proportion and keep layer structure constant, and also there is good structural complementarity. At the same time, these three transition metal ions are complementary also fine on chemical property.Three kinds of different metal ions play Different effects.Therefore, exploitation multielement composite positive pole is at one of research direction of anode material for lithium-ion batteries.
Although having succeeded commerce-change LiNi at present1/3Co1/3Mn1/3O2、LiNi0.4Co0.2Mn0.4O2、 LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2Tertiary cathode material, but they remain specific capacity relatively low, Co The shortcomings of content is higher, and cost is difficult to compress.The tertiary cathode material LiNi of rich ni-typexCoyMnl-x-yO2( x>0.6) compared to LiCoO2Actual discharge specific capacity is high, production cost is low and thermal stability and chemical stability also higher, is LiCoO2Material One of best replacer, possesses prodigious market potential and application prospect.Therefore, research and development LiNixCoyMnl-x-yO2 (X> 0.6) positive electrode has the development in developing anode material for lithium-ion batteries market, national economy of improving the ecological environment, promote There is important meaning.
Invention content
The purpose of the present invention is overcoming some shortcomings of existing anode material for lithium-ion batteries, improve relevant electrochemistry Performance improves energy density, reduces material cost etc..Novel nickelic tertiary cathode material of the invention a kind of and preparation, compared to Traditional material optimizes the ratio of three kinds of transition metal elements, with higher specific capacity and has taken into account excellent cycle Stability.
The purpose of the present invention is achieved through the following technical solutions:
A kind of novel nickelic tertiary cathode material, it is characterised in that:Molecular formula is LiNixCoyMnzO2, x+y+z=1, y≤0.1, 0.6<x<The content of tri- kinds of transition metal elements of 0.8, Ni, Co, Mn, which have passed through, to be optimized and revised, and product is spherical morphology, cation Mixing degree is low, surface crystal structure is stable, electrochemical performance.
Further, it be 0.1, z values is 0.22 that x values, which are 0.68, y values,.
A kind of preparation method of novel nickelic tertiary cathode material, it is characterised in that:Preparation process is as follows:
S1. coprecipitation prepares presoma:According to target the stoichiometric ratio of sample weighs analytically pure nickel salt, cobalt salt and manganese salt Be dissolved in deionized water formed reaction material liquid it is spare, take the monoacidic base of corresponding amount be dissolved in deionized water formed it is certain density molten Liquid is spare as precipitating reagent;Using four-hole boiling flask as reaction vessel, a certain amount of deionized water conduct is added into four-hole boiling flask Bottom liquid is reacted, reaction is sealed four-hole boiling flask before starting, is passed through the inert gas of a period of time in bottle, in venting reaction system Oxygen;When reacting beginning, suitable ammonium hydroxide is added in the liquid of bottom as complexing agent, by reaction material liquid and is sunk by separatory funnel Agent cocurrent in shallow lake is added in the liquid of bottom, and stirring is added dropwise for side until reaction terminates;After being aged a period of time, reaction solution, which takes out, to be filtered, and is obtained Filter cake filtering and washing for several times;Then the filter cake after washing is put into air dry oven, dry a period of time under certain temperature, Grinding is taken out, Ni is obtainedxCoyMnz(OH)2) spherical precursor;
S2. Rheological Phase Method is mixed with lithium salts stoichiometric ratio:The Ni that will be obtained in S1xCoyMnz(OH)2Spherical precursor with LiOH is 1 according to molar ratio:1.05 ratio mixing absolute ethyl alcohol or absolute methanol as dispersant, first room temperature magnetic agitation 1 ~ Then 3h is evaporated ethyl alcohol or methanol under water bath condition, powdery precursor is obtained after being fully ground;
S3. high-temperature calcination obtains product:The powdery precursor obtained in S2 is placed in Muffle furnace, lower 500 DEG C of air atmosphere is forged 5h is burnt, is ground after material furnace cooling, then is placed in tube furnace 750 ~ 850 DEG C of 12 ~ 20h of calcining under oxygen or ozone atmosphere.
Further, the nickel salt used in the step S1 is one kind in nickel sulfate, nickel chloride, nickel acetate, institute It is one kind in cobaltous sulfate, cobalt chloride, cobalt acetate to state cobalt salt, and the manganese salt is one kind in manganese sulfate, manganese chloride, manganese acetate.
Further, it is NaOH or KOH that the monoacidic base that the precipitating reagent uses is prepared in the step S1.
Further, the inert gas used in the step S1 is one kind in argon gas, nitrogen, helium.
Further, precipitating reagent described in the step S1 is to take the monoacidic base of corresponding amount to be dissolved in deionized water to be formed The solution of 2mol/L is made.
Further, the digestion time in the step S1 is 12h.
Further, the filter cake after washing is put into air dry oven in the step S1, is dried for 24 hours at 100 DEG C.
Further, the material after cooling and grinding is placed in tube furnace under oxygen or ozone atmosphere in the step S3 780 DEG C of calcining 16h.
The present invention has the following advantages:
Due to Ni content control 0.6 ~ 0.8, Co content control 0.1 hereinafter, therefore ensure that high power capacity, low cost Characteristic.In addition, by adjusting the stoichiometric ratio of Ni and Mn, cationic mixing degree, stabilizing material surface crystalline substance can also be reduced Body structure.Above-mentioned nickelic tertiary cathode material tap density ~ 3.5mg/cm3, reversible capacity is up to 200mAh/g, with excellent Cycle performance and high rate performance have broad application prospects as lithium ion battery with high energy density positive electrode.
The novel nickelic tertiary cathode material of one kind prepared by the method for the present invention as anode material for lithium-ion batteries in use, Compared to traditional material, the ratio of three kinds of transition metals is optimized, and has following advantage:(1)Crystal structure is more Add stabilization, cationic mixing degree lower;(2)Thermal stability and electrochemical stability are good, electrolyte resistance corrosion;(3)Product is Ball-type, tap density are high;(4)Reversible specific capacity is high(200mAh/g), cyclical stability and high rate performance are excellent.It can be extensive Positive field applied to 3C and batteries of electric automobile.
Description of the drawings
Fig. 1 is Ni0.68Co0.10Mn0.22(OH)2Spherical precursor SEM pictures;
Fig. 2 is LiNi0.68Co0.10Mn0.22O216h is calcined at 750 DEG C, presoma and LiOH proportionings are 1:1.05 SEM pictures;
Fig. 3 is LiNi0.68Co0.10Mn0.22O216h is calcined at 780 DEG C, presoma and LiOH proportionings are 1:1.05 SEM pictures;
Fig. 4 is LiNi0.68Co0.10Mn0.22O216h is calcined at 810 DEG C, presoma and LiOH proportionings are 1:1.05 SEM pictures;
Fig. 5 is LiNi0.68Co0.10Mn0.22O212h is calcined at 780 DEG C, presoma and LiOH proportionings are 1:1.05 SEM pictures;
Fig. 6 is LiNi0.68Co0.10Mn0.22O220h is calcined at 780 DEG C, presoma and LiOH proportionings are 1:1.05 SEM pictures;
Fig. 7 is LiNi0.68Co0.10Mn0.22O216h is calcined at 780 DEG C, presoma and LiOH proportionings are 1:1.03 SEM pictures;
Fig. 8 is LiNi0.68Co0.10Mn0.22O216h is calcined at 780 DEG C, presoma and LiOH proportionings are 1:1.07 SEM pictures;
Fig. 9 is the LiNi under different synthesis conditions0.68Co0.10Mn0.22O2It is tested under the current density of 1C (1C=0.2A/g) Constant current charge-discharge recycles;
Figure 10 is LiNi0.68Co0.10Mn0.22O216h is calcined at 780 DEG C, presoma and LiOH proportionings are 1:1.05 in different electricity The constant current charge-discharge cycle tested under current density 1/3C (0.066A/g), 1C (0.2A/g), 3C (0.6A/g) current density.
Specific implementation mode
The present invention will be further described below in conjunction with the accompanying drawings, but protection scope of the present invention is not limited to following institute It states.
A kind of preparation of novel nickelic tertiary cathode material of embodiment 1 includes the following steps:
S1. coprecipitation prepares presoma:According to target the stoichiometric ratio of sample weigh analytically pure nickel sulfate, cobaltous sulfate and Manganese sulfate, which is dissolved in deionized water, is used as reaction material liquid spare, takes the NaOH of corresponding amount to be dissolved in deionized water standby as precipitating reagent With;Using four-hole boiling flask as reaction vessel, a certain amount of deionized water is added into four-hole boiling flask as reaction bottom liquid, reaction is opened Be sealed four-hole boiling flask before beginning, when the argon gas of a period of time, the oxygen in venting reaction system are passed through in bottle;Reaction starts When, the suitable ammonium hydroxide of addition is (a concentration of by reaction material liquid and precipitating reagent by separatory funnel as complexing agent in the liquid of bottom The NaOH solution of 2mol/L) cocurrent be added bottom liquid in, be added dropwise side stirring until reaction terminates;After being aged a period of time, reaction solution It takes out and filters, obtained filter cake filtering and washing is for several times;Then the filter cake after washing is put into air dry oven, is done at 100 DEG C It is dry for 24 hours, take out grinding, obtain Ni0.68Co0.10Mn0.22(OH)2Spherical precursor.
S2. Rheological Phase Method matches lithium:The Ni that will be obtained in S10.68Co0.10Mn0.22(OH)2Spherical precursor and LiOH according to Molar ratio is 1:1.05 ratio is blended in a beaker, and a certain amount of absolute ethyl alcohol is added as dispersion into beaker Agent, first room temperature magnetic agitation 3h, is then evaporated under water bath condition, and powder body material is obtained after being fully ground.
S3. high-temperature calcination obtains product:The powder body material obtained in S2 is placed in lower 500 DEG C of air atmosphere in Muffle furnace 5h is calcined, is ground after material furnace cooling, 780 DEG C of calcining 16h under oxygen atmosphere, obtain in being placed in tube furnace LiNi0.68Co0.10Mn0.22O2
A kind of preparation of novel nickelic tertiary cathode material of embodiment 2 includes the following steps:
S1. coprecipitation prepares presoma:According to target the stoichiometric ratio of sample weigh analytically pure nickel sulfate, cobaltous sulfate and Manganese sulfate, which is dissolved in deionized water, is used as reaction material liquid spare, takes the NaOH of corresponding amount to be dissolved in deionized water standby as precipitating reagent With;Using four-hole boiling flask as reaction vessel, a certain amount of deionized water is added into four-hole boiling flask as reaction bottom liquid, reaction is opened Be sealed four-hole boiling flask before beginning, when the argon gas of a period of time, the oxygen in venting reaction system are passed through in bottle;Reaction starts When, the suitable ammonium hydroxide of addition is (a concentration of by reaction material liquid and precipitating reagent by separatory funnel as complexing agent in the liquid of bottom The NaOH solution of 2mol/L) cocurrent be added bottom liquid in, be added dropwise side stirring until reaction terminates;After being aged a period of time, reaction solution It takes out and filters, obtained filter cake filtering and washing is for several times;Then the filter cake after washing is put into air dry oven, is done at 100 DEG C It is dry for 24 hours, take out grinding, obtain Ni0.73Co0.05Mn0.22(OH)2Spherical precursor.
S2. Rheological Phase Method matches lithium:The Ni that will be obtained in S10.73Co0.05Mn0.22(OH)2Spherical precursor and LiOH according to Molar ratio is 1:1.05 ratio is blended in a beaker, and a certain amount of absolute ethyl alcohol is added as dispersion into beaker Agent, first room temperature magnetic agitation h, is then evaporated under water bath condition, and powder body material is obtained after being fully ground.
S3. high-temperature calcination obtains product:The powder body material obtained in S2 is placed in lower 500 DEG C of air atmosphere in Muffle furnace 5h is calcined, is ground after material furnace cooling, 780 DEG C of calcining 16h under oxygen atmosphere, obtain in being placed in tube furnace LiNi0.73Co0.05Mn0.22O2
A kind of preparation of novel nickelic tertiary cathode material of embodiment 3 includes the following steps:
S1. coprecipitation prepares presoma:According to target the stoichiometric ratio of sample weigh analytically pure nickel sulfate, cobaltous sulfate and Manganese sulfate, which is dissolved in deionized water, is used as reaction material liquid spare, takes the NaOH of corresponding amount to be dissolved in deionized water standby as precipitating reagent With;Using four-hole boiling flask as reaction vessel, a certain amount of deionized water is added into four-hole boiling flask as reaction bottom liquid, reaction is opened Be sealed four-hole boiling flask before beginning, when the argon gas of a period of time, the oxygen in venting reaction system are passed through in bottle;Reaction starts When, the suitable ammonium hydroxide of addition is (a concentration of by reaction material liquid and precipitating reagent by separatory funnel as complexing agent in the liquid of bottom The NaOH solution of 2mol/L) cocurrent be added bottom liquid in, be added dropwise side stirring until reaction terminates;After being aged a period of time, reaction solution It takes out and filters, obtained filter cake filtering and washing is for several times;Then the filter cake after washing is put into air dry oven, is done at 100 DEG C It is dry for 24 hours, take out grinding, obtain Ni0.64Co0.10Mn0.26(OH)2Spherical precursor.
S2. Rheological Phase Method matches lithium:The Ni that will be obtained in S10.64Co0.10Mn0.26(OH)2Spherical precursor and LiOH according to Molar ratio is 1:1.05 ratio is blended in a beaker, and a certain amount of absolute ethyl alcohol is added as dispersion into beaker Agent, first room temperature magnetic agitation 3h, is then evaporated under water bath condition, and powder body material is obtained after being fully ground.
S3. high-temperature calcination obtains product:The powder body material obtained in S2 is placed in lower 500 DEG C of air atmosphere in Muffle furnace 5h is calcined, is ground after material furnace cooling, 810 DEG C of calcining 16h under oxygen atmosphere, obtain in being placed in tube furnace LiNi0.64Co0.10Mn0.26O2
A kind of preparation of novel nickelic tertiary cathode material of embodiment 4 includes the following steps:
S1. coprecipitation prepares presoma:According to target the stoichiometric ratio of sample weigh analytically pure nickel sulfate, cobaltous sulfate and Manganese sulfate, which is dissolved in deionized water, is used as reaction material liquid spare, takes the NaOH of corresponding amount to be dissolved in deionized water standby as precipitating reagent With;Using four-hole boiling flask as reaction vessel, a certain amount of deionized water is added into four-hole boiling flask as reaction bottom liquid, reaction is opened Be sealed four-hole boiling flask before beginning, when the argon gas of a period of time, the oxygen in venting reaction system are passed through in bottle;Reaction starts When, the suitable ammonium hydroxide of addition is (a concentration of by reaction material liquid and precipitating reagent by separatory funnel as complexing agent in the liquid of bottom The NaOH solution of 2mol/L) cocurrent be added bottom liquid in, be added dropwise side stirring until reaction terminates;After being aged a period of time, reaction solution It takes out and filters, obtained filter cake filtering and washing is for several times;Then the filter cake after washing is put into air dry oven, is done at 100 DEG C It is dry for 24 hours, take out grinding, obtain Ni0.76Co0.05Mn0.19(OH)2Spherical precursor.
S2. Rheological Phase Method matches lithium:The Ni that will be obtained in S10.76Co0.05Mn0.19(OH)2Spherical precursor and LiOH according to Molar ratio is 1:1.05 ratio is blended in a beaker, and a certain amount of absolute ethyl alcohol is added as dispersion into beaker Agent, first room temperature magnetic agitation 3h, is then evaporated under water bath condition, and powder body material is obtained after being fully ground.
S3. high-temperature calcination obtains product:The powder body material obtained in S2 is placed in lower 500 DEG C of air atmosphere in Muffle furnace 5h is calcined, is ground after material furnace cooling, 750 DEG C of calcining 16h under oxygen atmosphere, obtain in being placed in tube furnace LiNi0.76Co0.05Mn0.19O2
A kind of preparation of novel nickelic tertiary cathode material of embodiment 5 includes the following steps:
S1. coprecipitation prepares presoma:According to target the stoichiometric ratio of sample weigh analytically pure nickel sulfate, cobaltous sulfate and Manganese sulfate, which is dissolved in deionized water, is used as reaction material liquid spare, takes the NaOH of corresponding amount to be dissolved in deionized water standby as precipitating reagent With;Using four-hole boiling flask as reaction vessel, a certain amount of deionized water is added into four-hole boiling flask as reaction bottom liquid, reaction is opened Be sealed four-hole boiling flask before beginning, when the argon gas of a period of time, the oxygen in venting reaction system are passed through in bottle;Reaction starts When, the suitable ammonium hydroxide of addition is (a concentration of by reaction material liquid and precipitating reagent by separatory funnel as complexing agent in the liquid of bottom The NaOH solution of 2mol/L) cocurrent be added bottom liquid in, be added dropwise side stirring until reaction terminates;After being aged a period of time, reaction solution It takes out and filters, obtained filter cake filtering and washing is for several times;Then the filter cake after washing is put into air dry oven, is done at 100 DEG C It is dry for 24 hours, take out grinding, obtain Ni0.79Co0.05Mn0.16(OH)2Spherical precursor.
S2. Rheological Phase Method matches lithium:The Ni that will be obtained in S10.79Co0.05Mn0.16(OH)2Spherical precursor and LiOH according to Molar ratio is 1:1.05 ratio is blended in a beaker, and a certain amount of absolute ethyl alcohol is added as dispersion into beaker Agent, first room temperature magnetic agitation 3h, is then evaporated under water bath condition, and powder body material is obtained after being fully ground.
S3. high-temperature calcination obtains product:The powder body material obtained in S2 is placed in lower 500 DEG C of air atmosphere in Muffle furnace 5h is calcined, is ground after material furnace cooling, 750 DEG C of calcining 20h under oxygen atmosphere, obtain in being placed in tube furnace LiNi0.79Co0.05Mn0.16O2
A kind of preparation of novel nickelic tertiary cathode material of embodiment 6 includes the following steps:
S1. coprecipitation prepares presoma:According to target the stoichiometric ratio of sample weigh analytically pure nickel sulfate, cobaltous sulfate and Manganese sulfate, which is dissolved in deionized water, is used as reaction material liquid spare, takes the NaOH of corresponding amount to be dissolved in deionized water standby as precipitating reagent With;Using four-hole boiling flask as reaction vessel, a certain amount of deionized water is added into four-hole boiling flask as reaction bottom liquid, reaction is opened Be sealed four-hole boiling flask before beginning, when the argon gas of a period of time, the oxygen in venting reaction system are passed through in bottle;Reaction starts When, the suitable ammonium hydroxide of addition is (a concentration of by reaction material liquid and precipitating reagent by separatory funnel as complexing agent in the liquid of bottom The NaOH solution of 2mol/L) cocurrent be added bottom liquid in, be added dropwise side stirring until reaction terminates;After being aged a period of time, reaction solution It takes out and filters, obtained filter cake filtering and washing is for several times;Then the filter cake after washing is put into air dry oven, is done at 100 DEG C It is dry for 24 hours, take out grinding, obtain Ni0.62Co0.10Mn0.28(OH)2Spherical precursor.
S2. Rheological Phase Method matches lithium:The Ni that will be obtained in S10.62Co0.10Mn0.28(OH)2Spherical precursor and LiOH according to Molar ratio is 1:1.05 ratio is blended in a beaker, and a certain amount of absolute ethyl alcohol is added as dispersion into beaker Agent, first room temperature magnetic agitation 3h, is then evaporated under water bath condition, and powder body material is obtained after being fully ground.
S3. high-temperature calcination obtains product:The powder body material obtained in S2 is placed in lower 500 DEG C of air atmosphere in Muffle furnace 5h is calcined, is ground after material furnace cooling, 850 DEG C of calcining 16h under oxygen atmosphere, obtain in being placed in tube furnace LiNi0.62Co0.10Mn0.28O2
The experimental results showed that suitable transition metal element proportioning calcination temperature and the proportioning of time and lithium salts are conducive to The optimization of the pattern and chemical property of material, with Ni0.68Co0.10Mn0.22(OH)2Spherical precursor is raw material, with lithium amount It is 1:1.05, the material by the high-temperature calcination of 780 DEG C of 16h has preferable pattern (Fig. 3) and optimal chemical property (Fig. 9 and Figure 10).As shown in Figure 9 780 degree of calcination temperature, the calcination time of 16h, 5wt% lithium amount of crossing be best synthesis item Part, the LiNi obtained under optimum synthesis condition as shown in Figure 100.68Co0.10Mn0.22O2Product has excellent high rate performance.
The above, only presently preferred embodiments of the present invention not do limitation in any form to the present invention.It is any ripe Those skilled in the art is known, without departing from the scope of the technical proposal of the invention, all using technology contents described above Many possible changes and modifications are made to technical solution of the present invention, or are revised as the equivalent embodiment of equivalent variations.Therefore, all It is the content without departing from technical solution of the present invention, any change modification made to the above embodiment of technology according to the present invention, Equivalent variations and modification belong to the protection domain of the technical program.

Claims (10)

1. a kind of novel nickelic tertiary cathode material, it is characterised in that:Molecular formula is LiNixCoyMnzO2, x+y+z=1, y≤ 0.1,0.6<x<The content of tri- kinds of transition metal elements of 0.8, Ni, Co, Mn, which have passed through, to be optimized and revised, and product is spherical morphology.
2. the novel nickelic tertiary cathode material of one kind according to claim 1, it is characterised in that:X values are that 0.68, y values are 0.1, z value is 0.22.
3. a kind of preparation method of novel nickelic tertiary cathode material according to one of claim 1-2, it is characterised in that: Preparation process is as follows:
S1. coprecipitation prepares presoma:According to target the stoichiometric ratio of sample weighs analytically pure nickel salt, cobalt salt and manganese salt Be dissolved in deionized water formed reaction material liquid it is spare, take the monoacidic base of corresponding amount be dissolved in deionized water formed it is certain density molten Liquid is spare as precipitating reagent;Using four-hole boiling flask as reaction vessel, a certain amount of deionized water conduct is added into four-hole boiling flask Bottom liquid is reacted, reaction is sealed four-hole boiling flask before starting, is passed through the inert gas of a period of time in bottle, in venting reaction system Oxygen;When reacting beginning, suitable ammonium hydroxide is added in the liquid of bottom as complexing agent, by reaction material liquid and is sunk by separatory funnel Agent cocurrent in shallow lake is added in the liquid of bottom, and stirring is added dropwise for side until reaction terminates;After being aged a period of time, reaction solution, which takes out, to be filtered, and is obtained Filter cake filtering and washing for several times;Then the filter cake after washing is put into air dry oven, dry a period of time under certain temperature, Grinding is taken out, Ni is obtainedxCoyMnz(OH)2) spherical precursor;
S2. Rheological Phase Method is mixed with lithium salts stoichiometric ratio:The Ni that will be obtained in S1xCoyMnz(OH)2Spherical precursor and LiOH It is 1 according to molar ratio:1.05 ratio mixing absolute ethyl alcohol or absolute methanol is as dispersant, 1 ~ 3h of first room temperature magnetic agitation, Then it is evaporated ethyl alcohol or methanol under water bath condition, powdery precursor is obtained after being fully ground;
S3. high-temperature calcination obtains product:The powdery precursor obtained in S2 is placed in Muffle furnace, lower 500 DEG C of air atmosphere is forged 5h is burnt, is ground after material furnace cooling, then is placed in tube furnace 750 ~ 850 DEG C of 12 ~ 20h of calcining under oxygen or ozone atmosphere.
4. a kind of preparation method of novel nickelic tertiary cathode material according to claim 3, it is characterised in that:The step The nickel salt used in rapid S1 is one kind in nickel sulfate, nickel chloride, nickel acetate, and the cobalt salt is cobaltous sulfate, cobalt chloride, second One kind in sour cobalt, the manganese salt are one kind in manganese sulfate, manganese chloride, manganese acetate.
5. a kind of preparation method of novel nickelic tertiary cathode material according to claim 3, it is characterised in that:The step It is NaOH or KOH that the monoacidic base that the precipitating reagent uses is prepared in rapid S1.
6. a kind of preparation method of novel nickelic tertiary cathode material according to claim 3, it is characterised in that:The step The inert gas used in rapid S1 is one kind in argon gas, nitrogen, helium.
7. a kind of preparation method of novel nickelic tertiary cathode material according to claim 3, it is characterised in that:The step Precipitating reagent described in rapid S1 is to take the monoacidic base of corresponding amount to be dissolved in deionized water to form the solution of 2mol/L to be made.
8. a kind of preparation method of novel nickelic tertiary cathode material according to claim 3, it is characterised in that:The step The digestion time in rapid S1 is 12h.
9. a kind of preparation method of novel nickelic tertiary cathode material according to claim 3, it is characterised in that:The step The filter cake after washing is put into air dry oven in rapid S1, is dried for 24 hours at 100 DEG C.
10. a kind of preparation method of novel nickelic tertiary cathode material according to claim 3, it is characterised in that:It is described The material after cooling and grinding is placed in oxygen or the lower 780 DEG C of calcinings 16h of ozone atmosphere in tube furnace in step S3.
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