CN114512660B - Positive active material precursor, preparation method thereof and positive active material - Google Patents

Positive active material precursor, preparation method thereof and positive active material Download PDF

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CN114512660B
CN114512660B CN202011286686.7A CN202011286686A CN114512660B CN 114512660 B CN114512660 B CN 114512660B CN 202011286686 A CN202011286686 A CN 202011286686A CN 114512660 B CN114512660 B CN 114512660B
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active material
precursor
positive electrode
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water
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CN114512660A (en
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武怿达
黄学杰
詹元杰
马晓威
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Institute of Physics of CAS
Songshan Lake Materials Laboratory
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Songshan Lake Materials Laboratory
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a precursor of a positive active material, the chemical molecular general formula of which is Ni 0.5‑x Mn 1.5‑y‑s A s (PO 4 ) z (B) u Wherein A is a non-lithium metal element and/or a metalloid element and B is OH ‑ Or CO 3 2‑ -0.2 x 0.2, -0.2 y 0.2,0 s 0.1,0.003 z 0.07 and 0.8 u 2.2, wherein the P elements in the precursor of the positive electrode active material are uniformly distributed in atomic scale. The invention also relates to a preparation method of the precursor of the positive active material, which comprises the steps of adding water-soluble phosphate, water-soluble nickel salt and water-soluble manganese salt into a reaction kettle, and controlling reaction conditions to realize coprecipitation of phosphorus, nickel and manganese metal ions. Furthermore, the invention also relates to a positive active material prepared by the positive active material precursor or the positive active material precursor obtained by the preparation method.

Description

Positive active material precursor, preparation method thereof and positive active material
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a precursor of a positive active material, the positive active material and a preparation method thereof.
Background
Compared with other rechargeable battery systems, the lithium ion secondary battery has the advantages of high working voltage, light weight, small volume, no memory effect, low self-discharge rate, long cycle life, high energy density and the like, and is widely applied to mobile terminal products such as mobile phones, notebook computers, tablet computers and the like. In recent years, environmental protection is consideredThe electric vehicle is rapidly developed under the push of governments and automobile manufacturers, and the lithium ion secondary battery becomes an ideal power source of a new generation of electric vehicles by virtue of excellent performance. Currently, positive active materials of lithium ion secondary batteries that are of interest can be roughly classified into three categories: with lithium cobaltate (LiCoO) 2 ) A layered material represented by lithium iron phosphate (LiFePO) 4 ) Olivine-type material typified by lithium manganate (LiMn) 2 O 4 ) Is a typical spinel structure material. Among these materials, spinel-structured materials have been widely studied because of their advantages of environmentally friendly raw materials, low cost, simple process, high safety, good rate capability, and the like.
A spinel-structured high-voltage material, which is an advanced positive active material, is considered to be the most likely positive active material for the next-generation high-performance lithium battery. In particular, the theoretical specific capacity of the lithium nickel manganese oxide with a spinel structure is 146.7mAh/g, and the working voltage is 4.7Vvs + The theoretical capacity density can reach 695Wh/kg, and the material is an ideal material for lithium ion secondary batteries for electric vehicles in the future.
In the circulating process of the high-voltage spinel cathode active material, because the traditional carbonate electrolyte interacts with the cathode active material, the surface of the cathode active material loses oxygen, the surface structure of the material is dissolved, and meanwhile, the surface defects gradually extend to a bulk phase, so that particles are broken, and finally the performance of the battery is rapidly reduced. In order to solve the technical problem, it is proposed to modify the cathode active material by doping elements, and the doped elements can form new chemical bonds in the material and on the surface so as to stabilize the bulk phase and the lattice oxygen on the surface, thereby solving the stability problem of the cathode active material interface and the bulk phase. The positive electrode active material is modified, for example, by doping with phosphorus element. In the traditional phosphorus element modification method, a nickel-manganese precursor synthesized by a coprecipitation method is mixed with a phosphorus source and a lithium source, and high-temperature sintering is carried out, so that the phosphorus element is difficult to modify the nickel-manganese acid lithium positive electrode material very uniformly.
Disclosure of Invention
Therefore, a positive active material precursor, a preparation method thereof and a positive active material are needed to be provided, so that phosphorus can be more uniformly distributed in the positive material precursor of the nickel lithium manganate, and finally, the phosphorus can uniformly modify the nickel lithium manganate, and the electrochemical performance of the positive material is improved.
The invention provides a precursor of a positive active material, the chemical molecular general formula of which is Ni 0.5-x Mn 1.5-y-s A s (PO 4 ) z (B) u Wherein A is a non-lithium metal element and/or a metalloid element, and B is OH - Or CO 3 2- X is more than or equal to 0.2 and less than or equal to 0.2, y is more than or equal to 0.2 and less than or equal to 0.2, s is more than or equal to 0 and less than or equal to 0.1, z is more than or equal to 0.003 and less than or equal to 0.07, and u is more than or equal to 0.8 and less than or equal to 2.2, and the P element in the precursor of the positive electrode active material is uniformly distributed.
In one embodiment, in the positive electrode active material precursor, s is 0, and the molar ratio of the elements Ni, mn, and P is 1: (2.5-3.5): (0.006-0.14).
In one embodiment, the non-lithium metal element is at least one selected from the group consisting of an alkaline earth metal element, a metalloid element, a transition metal element, and Al.
In one embodiment, A is selected from at least one of Al, mg, zn, fe, co, ti, Y, sc, ru, cu, mo, ge, W, zr, ca, nb, ta, sr.
In one embodiment, in the positive electrode active material precursor, the molar ratio of the elements Ni, mn, a, and P is 1: (2.5-3.5): (0.2-0.001): (0.06-0.2).
The invention further provides a preparation method of the precursor of the positive electrode active material, which comprises the following steps:
step a, providing an aqueous solution X of a complexing agent and an aqueous solution Y of an alkaline precipitator, and preparing a part of X and Y into a reaction kettle bottom solution;
b, mixing water-soluble nickel salt, manganese salt and water to form a mixed solution; the mixed solution optionally also contains at least one water-soluble non-lithium metal salt and/or metalloid element salt;
c, under the protection of inert gas, respectively adding the mixed solution and the water-soluble phosphate solution into a reaction kettle containing the reaction kettle bottom solution, and carrying out coprecipitation reaction under stirring, wherein the mixed solution and the water-soluble phosphate solution are fed at the same feeding speed, the balance of X and Y is added at the same time, the pH value of a reaction system and the concentration of the complexing agent are controlled by controlling the feeding amount of X and Y, and mixed slurry is obtained after the reaction is finished;
and d, aging, centrifuging, washing and drying the mixed slurry to obtain the precursor of the uniformly phosphorus-doped positive active material.
In one embodiment, the non-lithium metal salt is a sulfate, chloride or nitrate of any one of Al, mg, zn, fe, co, ti, Y, sc, ru, cu, mo, W, zr, ca, nb, ta and Sr, and the metalloid salt is a sulfate, chloride or nitrate of Ge.
In one embodiment, the concentration of phosphate ions in the water-soluble phosphate solution is 0.0025mol/L to 0.3mol/L, and the water-soluble phosphate is at least one of sodium phosphate, potassium phosphate, ammonium phosphate, sodium dihydrogen phosphate, lithium dihydrogen phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
In one embodiment, the complexing agent is at least one of hydrazine hydrate, crown ether, ammonia water, oxalic acid, ammonium bicarbonate, ethylenediamine and ethylenediamine tetraacetic acid, and the molar concentration of the complexing agent is 2-8 mol/L; the precipitant is NaOH, KOH, ba (OH) 2 、Na 2 CO 3 、Li 2 CO 3 、K 2 CO 3 Or LiOH, wherein the molar concentration of the precipitator is 2-6 mol/L.
In one embodiment, the pH of the reaction kettle bottom liquid is 10-12.5, and the concentration of the complexing agent in the reaction kettle bottom liquid is 15-20 g/L.
In a preferred embodiment, the pH of the reaction kettle bottoms is from 12 to 12.5.
In one embodiment, the reaction temperature of the coprecipitation reaction in the step c is 40-70 ℃, the pH of the reaction system is 10-12.5, the concentration of the complexing agent is 15-25 g/L, the stirring speed is 200-250 rpm, and the reaction time is 5-120 h.
In a preferred embodiment, the pH of the reaction system is 11.5 to 12.
In one embodiment, the total molar concentration of the metal ions in the mixed solution is 1 mol/L-3 mol/L, the water-soluble nickel salt is at least one of nickel sulfate, nickel chloride and nickel nitrate, and the water-soluble manganese salt is at least one of manganese sulfate, manganese chloride and manganese nitrate.
In one embodiment, the feeding speed of the mixed solution and the water-soluble phosphate is 0.1L/h-100L/h, the feeding speed of X is 0.1L/h-100L/h, and the feeding speed of Y is 0.1L/h-100L/h.
The invention further provides a positive electrode active material prepared from the positive electrode active material precursor or the positive electrode active material precursor prepared by the preparation method of the positive electrode active material precursor.
The precursor of the positive active material and the preparation method thereof provided by the invention have the advantages that the original properties of the nickel-manganese precursor are maintained, and the phosphorus element is uniformly distributed in the precursor in an atom level in a controllable manner on the basis of not influencing the element proportion. The precursor with the structure solves the problem that the subsequent traditional method adopts a high-temperature solid phase method to dope lithium and simultaneously dopes phosphorus difficultly and uniformly. By improving the performance of the precursor of the positive active material, the positive active material with more excellent performance and the lithium ion battery are prepared.
According to the preparation method of the precursor of the positive active material, provided by the invention, three elements of nickel, manganese and phosphorus are simultaneously and uniformly precipitated in the forms of nickel hydroxide, manganese hydroxide and phosphate radical by adopting a coprecipitation method to form the precursor of the positive active material. Adding water-soluble phosphate, water-soluble nickel salt and manganese salt into a reaction kettle, and controlling reaction conditions to realize coprecipitation of phosphorus, nickel and manganese metal ions. The water-soluble phosphate provides phosphate and nickel manganese ions to generate precipitates.
Drawings
Fig. 1 is an SEM sectional view of a positive electrode active material precursor prepared in example 1;
FIG. 2 is a SEM mapping distribution diagram of a cross section of a precursor of the positive active material prepared in example 1;
fig. 3 is an SEM mapping distribution diagram of a cross-section of a precursor of the positive electrode active material prepared in example 2.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art utilizing the teachings disclosed herein to achieve the desired properties. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
The embodiment of the invention provides a precursor of a positive active material, wherein the general formula of a chemical molecule of the precursor is Ni 0.5-x Mn 1.5-y-s A s (PO 4 ) z (B) u Wherein A is a non-lithium metal element and/or a metalloid element and B is OH - Or CO 3 2- ，-0.2≤x≤0.2，-0.2≤y is less than or equal to 0.2, s is less than or equal to 0 and less than or equal to 0.1, z is less than or equal to 0.003 and less than or equal to 0.07, u is less than or equal to 0.8 and less than or equal to 2.2, and the P element in the precursor of the positive electrode active material is uniformly distributed.
According to the precursor of the cathode active material provided by the embodiment of the invention, phosphorus elements are uniformly distributed in the precursor at an atomic level, and meanwhile, the precursor keeps the properties and element proportions of the traditional nickel-manganese precursor. The precursor with the structure solves the problem that the subsequent traditional method adopts a high-temperature solid phase method to dope lithium and simultaneously dopes phosphorus difficultly and uniformly. By improving the performance of the precursor of the positive active material, the positive active material with more excellent performance and the lithium ion battery are prepared.
In some embodiments, s is 0, and the chemical molecular formula of the positive electrode active material precursor is Ni 0.5- x Mn 1.5-y-s A s (PO 4 ) z (B) u Wherein A is a non-lithium metal element and/or a metalloid element and B is OH - Or CO 3 2- Wherein x is more than or equal to-0.2 and less than or equal to 0.2, y is more than or equal to-0.2 and less than or equal to 0.2, s is more than or equal to 0 and less than or equal to 0.2, z is more than or equal to 0.005 and less than or equal to 0.05, and u is more than or equal to 0.8 and less than or equal to 2.2.
Preferably, in the positive electrode active material precursor, the molar ratio of the elements Ni, mn, and P may be 1: (2.5-3.5): (0.006-0.14) in any ratio.
In other embodiments, s is not 0 and the non-lithium metal element a is selected from at least one of an alkaline earth metal element, a transition metal element, and Al.
Preferably, A is selected from at least one of Al, mg, zn, fe, co, ti, Y, sc, ru, cu, mo, ge, W, zr, ca, nb, ta, sr, B, si. More preferably, a is selected from at least one of Y, W, ti, mg, cu, ca and Al.
Further, in the above-described positive electrode active material precursor, the molar ratio of the elements Ni, mn, a, and P may be 1: (2.5-3.5): (0.2-0.001): (0.006-0.2) in any ratio.
The invention also provides a preparation method of the precursor of the positive active material, which comprises the following steps:
step a, providing an aqueous solution X of a complexing agent and an aqueous solution Y of an alkaline precipitator, and preparing a part of X and Y into a reaction kettle bottom solution;
b, mixing water-soluble nickel salt, manganese salt and water to form a mixed solution; the mixed solution optionally also contains at least one water-soluble non-lithium metal salt and/or metalloid element salt;
c, under the protection of inert gas, respectively adding the mixed solution and the water-soluble phosphate solution into a reaction kettle containing the reaction kettle bottom solution, and carrying out coprecipitation reaction under stirring, wherein the mixed solution and the water-soluble phosphate solution are fed at the same feeding speed, the rest of X and Y are added, the pH value of the reaction system and the concentration of the complexing agent are controlled by controlling the feeding amount of X and Y, and mixed slurry is obtained after the reaction is finished;
and d, aging, centrifuging, washing and drying the mixed slurry to obtain the precursor of the uniformly phosphorus-doped positive active material.
According to the preparation method of the precursor of the positive active material, provided by the invention, three elements of nickel, manganese and phosphorus are simultaneously and uniformly precipitated in the forms of nickel hydroxide, manganese hydroxide and phosphate radical by adopting a coprecipitation method to form the precursor of the positive active material. The phosphorus element is uniformly distributed in the positive electrode active material precursor at an atomic level.
The preparation principle of the precursor of the positive active material of the invention is as follows: adding water-soluble phosphate, water-soluble nickel salt and manganese salt into a reaction kettle, and controlling reaction conditions to realize coprecipitation of phosphorus, nickel and manganese metal ions. The water-soluble phosphate provides phosphate and nickel manganese ions to generate precipitates. In the preparation process, reaction conditions need to be strictly controlled, and the precursor of the positive active material is obtained through reaction, aging, centrifugation, washing and drying.
In some embodiments, the non-lithium metal salt may be a water-soluble sulfate, chloride, or nitrate salt of any one of an alkaline earth metal element, a transition metal element, and Al. Preferably, the non-lithium metal salt is a water-soluble sulfate, chloride or nitrate of at least one metal element of Al, mg, zn, fe, co, ti, Y, sc, ru, cu, mo, ge, W, zr, ca, nb, ta, sr, B, si. More preferably, the non-lithium metal salt is a water-soluble sulfate, chloride or nitrate of any one of Y, W, ti, mg, cu, ca and Al.
In some embodiments, the metalloid element salt is preferably a sulfate, chloride or nitrate salt of Ge.
The complexing agent can be at least one of hydrazine hydrate, crown ether, ammonia water, oxalic acid, ammonium bicarbonate, ethylenediamine and ethylenediamine tetraacetic acid. Preferably aqueous ammonia. The molar concentration of the complexing agent in X may be any value between 2mol/L and 8mol/L, and may be, for example, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, or 7.5mol/L.
The precipitant can be NaOH, KOH, ba (OH) 2 、Na 2 CO 3 、Li 2 CO 3 、K 2 CO 3 Or LiOH. NaOH is preferred. The molar concentration of the precipitant in Y may be any value from 2mol/L to 6mol/L, and may be 2.5mol/L, 3mol/L, 3.2mol/L, 3.5mol/L, 3.8mol/L, 4mol/L, 4.2mol/L, 4.5mol/L, 4.8mol/L, 5mol/L, or 5.5mol/L.
The pH of the reaction kettle bottom solution may be any value between 10 and 12.5, preferably between 12 and 12.5.
The concentration of the complexing agent in the reaction kettle bottom liquid can be any value between 15g/L and 20g/L, and can be 16g/L, 17g/L, 18g/L and 19g/L, for example.
The water-soluble nickel salt can be at least one of nickel sulfate, nickel chloride and nickel nitrate.
The water-soluble manganese salt can be at least one of manganese sulfate, manganese chloride and manganese nitrate.
The water-soluble phosphate can be at least one of sodium phosphate, sodium monohydrogen phosphate, potassium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, ammonium phosphate, sodium dihydrogen phosphate, lithium dihydrogen phosphate, ammonium monohydrogen phosphate, phosphoric acid and ammonium dihydrogen phosphate.
The total molar concentration of the metal ions in the mixed solution is 1-3 mol/L.
The concentration of phosphate ions in the water-soluble phosphate solution is 0.0025 mol/L-0.3 mol/L.
In the step c, the feeding speed of the mixed solution and the water-soluble phosphate is 0.1 mL/h-100 mL/h, the feeding speed of X is 0.1 mL/h-100 mL/h, and the feeding speed of Y is 0.1 mL/h-100 mL/h.
In the coprecipitation reaction process, the reaction temperature can be 40-70 ℃, the pH of the reaction system is controlled to be 10-12.5, more preferably 11.5-12, the concentration of the complexing agent is controlled to be 15-25 g/L, the stirring speed can be 200-250 rpm, and the reaction time can be 80-120 h.
Further, during the coprecipitation reaction, the pH of the reaction system is preferably controlled to 12.
The inert gas may be nitrogen.
In the step d, the aging time of the mixed slurry can be 20 hours to 24 hours, and the aging temperature can be 15 ℃ to 80 ℃.
The invention further provides a positive electrode active material prepared from the positive electrode active material precursor or the positive electrode active material precursor obtained by the preparation method of the positive electrode active material precursor.
The invention further provides a preparation method of the positive active material, which comprises the following steps:
mixing the positive electrode active material precursor or the positive electrode active material precursor obtained by the preparation method of the positive electrode active material precursor with a lithium source;
sintering for 5-10 hours at 600-1200 ℃ in an oxygen-containing atmosphere.
The lithium source is lithium carbonate or lithium hydroxide, and lithium carbonate is preferred.
The sintering may be performed in an oxygen atmosphere such as oxygen or air. Preferably, the specific operation of the sintering process is as follows: heating to 600-1200 ℃ at the heating rate of 0.5-10 ℃/min, then sintering for 0.5-10 h, and then cooling to room temperature at the cooling rate of 0.5-10 ℃/min.
The precursor of the positive active material is doped with phosphorus elements, the precursor of the positive active material contained in the invention can be cut by a laser ion beam cutting method, and the uniform distribution condition of the phosphorus elements in the positive active material is represented by an SEM mapping, TEM-mapping or XPS photoelectron imaging method, so that the characteristics of the precursor of the positive active material contained in the invention are further determined.
The invention also provides a positive electrode of the lithium ion secondary battery, which comprises a positive electrode current collector and a positive electrode active material layer positioned on the positive electrode current collector, wherein the positive electrode active material layer comprises the positive electrode active material.
As the positive electrode current collector, a conductive member formed of a highly conductive metal as used in a positive electrode of a lithium ion secondary battery of the related art is preferable. For example, aluminum or an alloy including aluminum as a main component may be used. The shape of the positive electrode current collector is not particularly limited, since it may vary depending on the shape of the lithium ion secondary battery, etc. For example, the positive electrode collector may have various shapes such as a rod shape, a plate shape, a sheet shape, and a foil shape.
The positive active material layer further includes a conductive additive and a binder.
The conductive additive may be a conductive additive that is conventional in the art, and the present invention is not particularly limited thereto. For example, in some embodiments, the conductive additive is carbon black (e.g., acetylene black or Ketjen black).
The binder may be a binder conventional in the art, and the present invention is not particularly limited thereto, and may be composed of polyvinylidene fluoride (PVDF), or carboxymethyl cellulose (CMC) and styrene-butadiene rubber (SBR). In some embodiments, the binder is polyvinylidene fluoride (PVDF).
The present invention also provides a lithium ion secondary battery comprising:
the positive electrode as described above;
a negative electrode including a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector;
a separator and an electrolyte.
As a current collector of the negative electrode,
the negative electrode, separator and electrolyte may employ negative electrode current collectors, separators and electrolyte materials that are conventional in the art, and the present invention is not particularly limited thereto.
The negative electrode current collector may be copper, and the shape of the negative electrode current collector is also not particularly limited, and may be rod-shaped, plate-shaped, sheet-shaped, and foil-shaped, and may vary depending on the shape of the lithium ion secondary battery, and the like. The negative active material layer includes a negative active material, a conductive additive, and a binder. The negative active material, conductive additive and binder are also conventional in the art. In some embodiments, the negative active material is metallic lithium. The conductive additive and the binder are as described above and will not be described in detail herein.
The separator may be a separator used in a general lithium ion secondary battery, and examples thereof include a microporous film made of polyethylene or polypropylene; a multi-layer film of a porous polyethylene film and polypropylene; nonwoven fabrics formed of polyester fibers, aramid fibers, glass fibers, and the like; and a base film formed by adhering ceramic fine particles such as silica, alumina, and titania to the surfaces thereof. In some embodiments, the separator is a three layer film of PP/PE/PP coated on both sides with alumina.
The electrolyte may include an electrolyte and a non-aqueous organic solvent. The electrolyte is preferably LiPF 6 、LiBF 4 、LiSbF 6 、LiAsF 6 . The non-aqueous organic solvent can be carbonate, ester and ether. Among them, carbonates such as Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and ethylmethyl carbonate (EMC) can be preferably used. In some embodiments, the electrolyte is LiPF 6 The concentration of (2) is 1mol/L of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) non-aqueous electrolyte, wherein the volume ratio of EC to DMC is 1.
The following are specific examples, which are intended to provide further detailed description of the present invention and to assist those skilled in the art and researchers in understanding the present invention, and the technical conditions and the like are not intended to limit the present invention. Any modification made within the scope of the claims of the present invention is within the scope of the claims of the present invention.
The following examples are intended to illustrate the present invention in further detail to help those skilled in the art and researchers understand the present invention, and the technical conditions and the like are not to be construed as limiting the present invention. Any modification made within the scope of the claims of the present invention is within the scope of the claims of the present invention.
Example 1
(1) Preparing a sodium hydroxide solution with the concentration of 5mol/L and ammonia water with the concentration of 6mol/L, and mixing part of the sodium hydroxide solution and the ammonia water to prepare a solution with the pH =12 and the ammonia concentration of 15g/L as a reaction kettle bottom solution.
(2) According to the molar ratio of Ni: mn: p is 1:3:0.02, nickel sulfate, manganese sulfate and ammonium dihydrogen phosphate are weighed, the nickel sulfate and the manganese sulfate are dissolved in water to prepare a mixed solution with the total metal ion concentration of 1mol/L, and the ammonium dihydrogen phosphate is dissolved in water to prepare a water-soluble phosphate solution with the phosphate ion concentration of 0.02 mol/L.
(3) And (2) introducing nitrogen into the reaction kettle filled with the base solution C, under the protection of the nitrogen, adding the mixed solution and the water-soluble phosphate solution in the step (2) into the reaction kettle at a feeding speed of 0.5L/h, adding the sodium hydroxide solution at a feeding speed of 0.5L/h and the ammonia water at a feeding speed of 0.5L/h, feeding through a metering pump, controlling the pH of the reaction system to be 12 and the ammonia concentration to be 15g/L in the feeding process, carrying out coprecipitation reaction at 40 ℃ and a stirring speed of 200rpm, and reacting for 100 hours to obtain mixed slurry.
(4) And transferring the mixed slurry to an ageing tank for ageing, centrifuging, washing and drying to obtain the uniform phosphorus-doped anode active material precursor, wherein the ageing temperature is 70 ℃, and the ageing time is 80 hours.
Fig. 1 shows a laser ion beam cutting picture of the precursor of the uniformly phosphorus-doped positive electrode active material prepared in this example.
FIG. 2 is a scanning electron microscope element mapping distribution diagram of the precursor of the uniformly phosphorus-doped positive active material obtained after cutting by laser ion beams. As can be seen from fig. 2, the phosphorus is uniformly distributed inside the precursor.
Example 2
(1) Preparing 5mol/L carbonic acid solution and 6mol/L ammonia water, mixing part of sodium hydroxide solution and ammonia water to prepare solution with pH =10.8 and ammonia concentration of 15g/L as the bottom solution of the reaction kettle.
(2) According to a molar ratio of Ni: mn: p is 1:3:0.02, nickel sulfate, manganese sulfate and ammonium dihydrogen phosphate are weighed, the nickel sulfate and the manganese sulfate are dissolved in water to prepare a mixed solution with the total metal ion concentration of 1mol/L, and the ammonium dihydrogen phosphate is dissolved in water to prepare a water-soluble phosphate solution with the phosphate radical ion concentration of 0.02 mol/L.
(3) And (2) introducing nitrogen into the reaction kettle filled with the base solution C, adding the mixed solution and the water-soluble phosphate solution into the reaction kettle at a feeding speed of 0.5L/h, adding the sodium hydroxide solution at a feeding speed of 0.5L/h and the ammonia water at a feeding speed of 0.5L/h under the protection of the nitrogen, feeding the mixed solution through a metering pump, controlling the pH of the reaction system to be 10.8 and the ammonia concentration to be 15g/L in the feeding process, carrying out coprecipitation reaction at 40 ℃ and at a stirring speed of 200rpm for 100 hours to obtain mixed slurry.
(4) And transferring the mixed slurry to an ageing tank for ageing, centrifuging, washing and drying to obtain the uniformly phosphorus-doped anode active material precursor, wherein the ageing temperature is 60 ℃, and the ageing time is 20 hours.
FIG. 3 is a scanning electron microscope element mapping distribution diagram of the precursor of the uniformly phosphorus-doped positive active material obtained after cutting by laser ion beams. As can be seen from fig. 3, the phosphorus is uniformly distributed inside the precursor.
Example 3
And grinding and mixing 10g of the precursor synthesized in the embodiment 1 and 2.169g of lithium carbonate, and placing the mixture in a furnace at 950 ℃ for high-temperature calcination for 20 hours, wherein the heating rate is 3 ℃/min and the cooling rate is 5 ℃/min, so as to obtain the sintered lithium nickel manganese oxide cathode material uniformly doped with phosphorus elements.
Comparative example 1
Taking 10g of Ni 0.5 Mn 1.5 (OH) 4 0.064g of diammonium hydrogen phosphate and 2.169g of lithium carbonate are ground and mixed, and the mixture is placed in a furnace at 950 ℃ for high-temperature calcination for 20 hours, wherein the temperature rise rate is 3 ℃/min and the temperature drop rate is 5 ℃/min, and the same phosphorus as in example 3 is obtained after sinteringThe content of the doped lithium nickel manganese oxide cathode material.
The positive active materials prepared in example 3 and comparative example 1 were assembled into a button cell according to the following procedure.
(1) Preparation of Positive electrode sheet
The positive electrode active material prepared in the examples, carbon black as a conductive additive, and polyvinylidene fluoride (PVDF) as a binder were dispersed in N-methylpyrrolidone (NMP) at a weight ratio of 80. Uniformly coating the uniform positive electrode slurry on an aluminum foil current collector with the thickness of 15 mu m, drying at 55 ℃ to form a pole piece with the thickness of 100 mu m, and rolling the pole piece under a roller press (the pressure is about 1MPa multiplied by 1.5 cm) 2 ) Cutting the anode plate into round pieces with the diameter of 14mm, then placing the round pieces in a vacuum oven to be dried for 6 hours at the temperature of 120 ℃, naturally cooling the round pieces, taking out the round pieces and placing the round pieces in a glove box to be used as anode pieces.
(2) Assembling lithium ion secondary battery
And (2) in a glove box filled with inert atmosphere, placing metal lithium as a negative electrode of the battery, taking a PP/PE/PP three-layer film coated with aluminum oxide on two sides as a diaphragm between the positive electrode and the negative electrode, dropwise adding common carbonate electrolyte, taking the positive electrode plate prepared in the step (1) as a positive electrode, and assembling into a button battery with the model of CR 2032.
High-temperature cycle test:
and standing the prepared button cell for 10 hours at room temperature (25 ℃), then carrying out charge-discharge activation on the button cell, and then carrying out charge-discharge cycle test on the prepared button cell by adopting a blue cell charge-discharge tester. The method comprises the steps of firstly cycling at a rate of 0.1C for 1 week under the condition of room temperature (25 ℃), and then continuing cycling at a rate of 0.2C for 4 weeks, wherein the charging and discharging voltage range of the battery is controlled to be 3.5V-4.9V. Then, the button cell is transferred to a high-temperature environment of 55 ℃, the circulation is continued for 50 weeks at the multiplying power of 0.2C, and the charging and discharging voltage range of the cell is still controlled to be 3.5V-4.9V.
TABLE 1 electrochemical Properties of Positive electrode active Material of examples of the present invention
Figure BDA0002782564800000121
As can be seen from table 1, the electrochemical performance of the cathode active material prepared from the precursor material prepared in example 1 is significantly better than that of the lithium nickel manganese oxide cathode material doped with the same phosphorus content in comparative example 1.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (16)

1. A precursor of positive active material is characterized in that the general formula of the chemical molecule is Ni 0.5-x Mn 1.5-y-s A s (PO 4 ) z (B) u Wherein A is a non-lithium metal element and/or a metalloid element, and B is OH - Or CO 3 2- X is more than or equal to 0.2 and less than or equal to 0.2, y is more than or equal to 0.2 and less than or equal to 0.2, s is more than or equal to 0 and less than or equal to 0.1, z is more than or equal to 0.003 and less than or equal to 0.07, and u is more than or equal to 0.8 and less than or equal to 2.2, and the P element in the precursor of the positive electrode active material is uniformly distributed.
2. The positive electrode active material precursor according to claim 1, wherein s is 0, and the molar ratio of the elements Ni, mn, and P is 1: (2.5 to 3.5): (0.006 to 0.14).
3. The positive electrode active material precursor according to claim 1, wherein the non-lithium metal element is at least one selected from the group consisting of an alkaline earth metal element, a transition metal element, and Al.
4. The positive electrode active material precursor according to any one of claims 1 to 3, wherein A is at least one selected from Al, mg, zn, fe, co, ti, Y, sc, ru, cu, mo, ge, W, zr, ca, nb, ta, and Sr.
5. The positive electrode active material precursor according to claim 1, wherein the molar ratio of the elements Ni, mn, a, and P in the positive electrode active material precursor is 1: (2.5 to 3.5): (0.2 to 0.001): (0.006 to 0.2).
6. A method for preparing a precursor of a positive electrode active material is characterized by comprising the following steps:
step a, providing an aqueous solution X of a complexing agent and an aqueous solution Y of an alkaline precipitator, and preparing a part of X and Y into a reaction kettle bottom solution;
step b, mixing water-soluble nickel salt, water-soluble manganese salt and water to form a mixed solution; the mixed solution optionally contains at least one water-soluble non-lithium metal salt and/or metalloid element salt;
c, under the protection of inert gas, respectively adding the mixed solution and the water-soluble phosphate solution into a reaction kettle containing the reaction kettle bottom solution, and carrying out coprecipitation reaction under stirring, wherein the mixed solution and the water-soluble phosphate solution are fed at the same feeding speed, the balance of X and Y is added at the same time, the pH value of a reaction system and the concentration of the complexing agent are controlled by controlling the feeding amount of X and Y, and mixed slurry is obtained after the reaction is finished;
and d, aging, centrifuging, washing and drying the mixed slurry to obtain the precursor of the uniformly phosphorus-doped positive active material.
7. The method for producing a precursor of a positive electrode active material according to claim 6, wherein the non-lithium metal salt is a sulfate, chloride or nitrate of any one of Al, mg, zn, fe, co, ti, Y, sc, ru, cu, mo, W, zr, ca, nb, ta and Sr, and the metalloid salt is a sulfate, chloride or nitrate of Ge.
8. The method for producing a precursor of a positive electrode active material according to claim 6, wherein the concentration of phosphate ions in the water-soluble phosphate solution is 0.0025mol/L to 0.3mol/L, and the water-soluble phosphate is at least one of sodium phosphate, sodium monohydrogen phosphate, potassium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate, ammonium phosphate, sodium dihydrogen phosphate, lithium dihydrogen phosphate, ammonium monohydrogen phosphate, phosphoric acid, and ammonium dihydrogen phosphate.
9. The method for preparing a precursor of a positive electrode active material according to claim 6, wherein the complexing agent is at least one of hydrazine hydrate, crown ether, ammonia water, oxalic acid, ammonium bicarbonate, ethylenediamine and ethylenediamine tetraacetic acid, and the molar concentration of the complexing agent is 2mol/L to 8mol/L; the precipitant is NaOH, KOH, ba (OH) 2 、Na 2 CO 3 、Li 2 CO 3 、K 2 CO 3 Or LiOH, wherein the molar concentration of the precipitant is 2-6 mol/L.
10. The method for preparing a precursor of a positive electrode active material according to claim 6, wherein the reaction vessel bottom solution has a pH of 10 to 12.5, and the concentration of the complexing agent in the reaction vessel bottom solution is 15g/L to 20g/L.
11. The method for producing the precursor of the positive electrode active material according to claim 10, wherein the reaction kettle base solution has a pH of 12 to 12.5.
12. The method for preparing the precursor of the positive electrode active material according to claim 6, wherein the reaction temperature of the coprecipitation reaction in the step c is 40 to 70 ℃, the pH of the reaction system is 10 to 12.5, the concentration of the complexing agent is 15 to 25g/L, the stirring speed is 200 to 250rpm, and the reaction time is 5 to 120 hours.
13. The method for producing a precursor for a positive electrode active material according to claim 12, wherein the reaction system has a pH of 11.5 to 12.
14. The method for preparing a precursor of a positive electrode active material according to claim 6, wherein the total molar concentration of metal ions in the mixed solution is 1mol/L to 3mol/L, the water-soluble nickel salt is at least one of nickel sulfate, nickel chloride and nickel nitrate, and the water-soluble manganese salt is at least one of manganese sulfate, manganese chloride and manganese nitrate.
15. The method for preparing a precursor of a positive electrode active material according to claim 6, wherein the feed rate of the mixed solution and the water-soluble phosphate is 0.1L/h to 100L/h, the feed rate of X is 0.1L/h to 100L/h, and the feed rate of Y is 0.1L/h to 100L/h.
16. A positive electrode active material produced from the positive electrode active material precursor according to any one of claims 1 to 5 or the positive electrode active material precursor produced by the method for producing a positive electrode active material precursor according to any one of claims 6 to 13.
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CN103107325A (en) * 2011-11-11 2013-05-15 Skc株式会社 Cathode active material for a lithium secondary battery containing phosphate fluoride and preparation method thereof
CN103779556A (en) * 2014-01-26 2014-05-07 中信国安盟固利电源技术有限公司 Doped and surface coating co-modified anode material for lithium ion battery and preparation method thereof
CN109360984A (en) * 2018-12-06 2019-02-19 济南大学 A kind of preparation method on layered cathode material of lithium ion battery hydridization surface

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103107325A (en) * 2011-11-11 2013-05-15 Skc株式会社 Cathode active material for a lithium secondary battery containing phosphate fluoride and preparation method thereof
CN103779556A (en) * 2014-01-26 2014-05-07 中信国安盟固利电源技术有限公司 Doped and surface coating co-modified anode material for lithium ion battery and preparation method thereof
CN109360984A (en) * 2018-12-06 2019-02-19 济南大学 A kind of preparation method on layered cathode material of lithium ion battery hydridization surface

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