CN109994726A - A kind of positive electrode material precursor and preparation method thereof, positive electrode and lithium ion battery - Google Patents

A kind of positive electrode material precursor and preparation method thereof, positive electrode and lithium ion battery Download PDF

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CN109994726A
CN109994726A CN201711481516.2A CN201711481516A CN109994726A CN 109994726 A CN109994726 A CN 109994726A CN 201711481516 A CN201711481516 A CN 201711481516A CN 109994726 A CN109994726 A CN 109994726A
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positive electrode
salt
material precursor
electrode material
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CN109994726B (en
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陈建生
周云鹏
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Hubei Nine New Energy Technology Co Ltd Of Nation
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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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention provides a kind of positive electrode material precursors, have the general formula as shown in formula (I): NixCoyMnzAl1‑x‑y‑z(OH)2(I)；The positive electrode material precursor is the spheric granules of six square piece of positive electrode material precursor composition, and is compounded with positive electrode material precursor nano particle in six square piece of the positive electrode material precursor.The present invention has obtained the presoma of ternary or quaternary positive electrode, spheric granules is formed by six square pieces, and the nano particle of presoma is also compounded in six square piece of presoma, the hexagonal flake of these multilayers and its nano particle on surface form spherical particle, structural integrity is uniform, the nano particle on hexagonal flake surface can be effectively improved positive electrode processing performance, improve cathode material structure stability, improve positive electrode cycle performance, the nano particle on hexagonal flake surface also increases the specific surface area of material, reduce the internal resistance during material circulation, improve the high rate performance of material.

Description

A kind of positive electrode material precursor and preparation method thereof, positive electrode and lithium ion battery
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of positive electrode material precursor and preparation method thereof, Positive electrode and lithium ion battery.
Background technique
Lithium ion battery generally includes anode, cathode, diaphragm, electrolyte and shell, has operating voltage height, specific energy It is high, have extended cycle life, be light-weight, self discharge is few, memory-less effect and cost performance ratio, it has also become high power is electronic The main selecting object of the fields such as vehicle, artificial satellite, aerospace rechargeable type power supply.In all components of lithium ion battery In, especially after invention hyperconcetration electrolyte, electrode material is always to improve the main bottleneck of its energy density, anode be lithium from One of sub- battery critical material, decides the performance of lithium ion battery, therefore is also always the research hotspot of scientific research personnel.Lithium from The anode of sub- battery, i.e. positive plate generally include positive electrode active materials, conductive agent, binder, solvent and collector, among these most What it is for key is exactly positive electrode active materials.Start within especially 2015, new-energy automobile industry welcomes comprehensive outbreak period, with tradition Automobile is compared, and is always new-energy automobile due to the cruising ability and safety of the new-energy automobile that power battery decides The core of producer and consumer's concern；The course continuation mileage of vehicle is promoted, key is to promote the energy density of power battery, more next More battery manufacturers starts the R&D work of Efforts To Develop high-energy density power battery.
In current power lithium-ion battery positive electrode, nickle cobalt lithium manganate tertiary cathode material (NCM) and nickel cobalt aluminium Sour lithium tertiary cathode material (NCA) has energy density height, cost is relatively low and environment friend due to the synergistic effect of three kinds of elements The advantages that good, becomes the great positive electrode active materials of world market power lithium-ion battery application field increment in recent years.With For NCM, when voltage is within the scope of 3.0~4.3V, although having longer period and cycle life, specific capacitance is only 130~150mA/hg.By lasting research in the industry, in recent years it is reported that, when the increase of the material cell capacity, not shadow Its service life, thus ternary NCM positive electrode are rung, has caused academia and industry greatly emerging in terms of improving gram volume Interest.Such as anionic/cationic doping, the design of coating, concentration gradient.But the reality of the ternary NCM material after improveing Capacity is still below 200mA/hg, and the structural stability of the ternary NCM material after improvement and cycle performance are undesirable, especially tie Structure stability will appear decline.
Therefore, the structural stability, battery capacity and electrochemistry cycle performance etc. of tertiary cathode material how to be solved The problem of, it has also become an all multi-vendor in the industry and line researcher widely one of focus of attention.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of positive electrode material precursor and its preparation side Method.The positive electrode of positive electrode material precursor preparation provided by the invention is used for lithium ion battery, stable structure with higher Property and battery capacity, and preferable electrochemistry cycle performance.Meanwhile preparation method simple process provided by the invention, condition Mildly, it is suitable for large-scale production and application.
The present invention provides a kind of positive electrode material precursors, have the general formula as shown in formula (I):
NixCoyMnzAl1-x-y-z(OH)2(I)；
Wherein, 0 < x < 1,0 < y < 1, x+y < 1,0≤z < 1, x+y+z≤1；
The spheric granules that the positive electrode material precursor forms for six square piece of positive electrode material precursor, and the positive electrode Positive electrode material precursor nano particle is compounded in six square piece of presoma.
Preferably, six square pieces of the positive electrode material precursor include the layered body of six square piece of multilayer composition, or, multilayer six Six square piece of layered body and single layer of square piece composition；
The number of plies of the multilayer is 2~50 layers；
The partial size of the nano particle is 100~300nm；
The mass ratio of six square piece of positive electrode material precursor and the positive electrode material precursor nano particle be 10:(1~ 5)。
Preferably, become stacking formation for described group；
Six square piece of multilayer with a thickness of 50~200nm；
The piece interlayer of six square piece of multilayer has gap；
The positive electrode material precursor nano-particles reinforcement is on the surface and piece lamellar spacing of six square piece of multilayer.
The present invention provides a kind of preparation methods of positive electrode material precursor, comprising the following steps:
1) after mixing nickel salt, manganese salt and/or aluminium salt, cobalt salt and water, mixed liquor is obtained；
2) mixed liquor, complexing agent and alkali is added, after being reacted, obtains the first mixed solution；
3) into the first mixed solution that above-mentioned steps obtain, mixed liquor, complexing agent and alkali, then secondary response are continuously added Afterwards, the second mixed solution is obtained；
4) the second mixed solution for obtaining above-mentioned steps obtains positive electrode material precursor after ageing.
Preferably, the step 1) specifically:
After nickel salt, manganese salt, cobalt salt and water are mixed, just mixed liquor is obtained；
After aluminium salt and water are mixed, aluminum salt solution is obtained；The molar concentration of the aluminum salt solution is 0.1~2mol/L；
After first mixed liquor and aluminum salt solution are mixed, mixed liquor is obtained.
Preferably, in the mixed liquor, the total mol concentration of the manganese salt and/or aluminium salt, nickel salt and cobalt salt is 1~ 3.5mol/L；
The alkali is selected from one of lithium hydroxide, sodium hydroxide and potassium hydroxide or a variety of；
The complexing agent is selected from ammonium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, nitric acid One of ammonium and urea are a variety of；
In the step 2), the molal quantity of the complexing agent and the nickel salt, manganese salt and/or aluminium salt, the total moles of cobalt salt Several ratio is (1~10): 1；
The pH value of the reaction is 7.5~12.0；
The time of the reaction is 4~36h；
The temperature of the reaction is 40~70 DEG C.
Preferably, in the step 3), the molal quantity of the complexing agent and the nickel salt, manganese salt and/or aluminium salt, cobalt salt The ratio of total mole number is (5~20): 1；
The pH value of the secondary response again is 9.5~13.0；
The pH value of the secondary response again is higher than the pH value of reaction by 0.25~2；
The time of the secondary response again is 36~50h；
The temperature of the secondary response again is 45~65 DEG C；
The time of the ageing is 20~40h.
The present invention provides a kind of positive electrodes, have the general formula as shown in formula (II):
Li1+wNixCoyMnzAl1-x-y-zO2(II),
Wherein, 0 < x < 1,0 < y < 1, x+y < 1,0≤z < 1, x+y+z≤1, -0.5≤w≤0.5；
The positive electrode is the spheric granules of six square piece of positive electrode composition, and compound in six square piece of the positive electrode There is positive electrode nano particle.
Preferably, positive electrode positive electrode material precursor as described in above-mentioned technical proposal any one or above-mentioned skill Positive electrode material precursor prepared by preparation method described in art scheme any one is after heat treatment obtained with lithium salts；
The temperature of the heat treatment is 725 DEG C~1150 DEG C.
The present invention also provides a kind of lithium ion batteries, including positive electrode described in above-mentioned technical proposal any one.
The present invention provides a kind of positive electrode material precursors, have the general formula as shown in formula (I): NixCoyMnzAl1-x-y-z (OH)2(I)；Wherein, 0 < x < 1,0 < y < 1,0≤z < 1, x+y+z≤1；The positive electrode material precursor is positive electrode material precursor The spheric granules of six square pieces composition, and positive electrode material precursor nanometer is compounded in six square piece of the positive electrode material precursor Grain.Compared with prior art, the present invention for the capacity of the ternary material after existing improvement is lower and structural stability and The undesirable problem of cycle performance.The present invention starts with from the presoma of positive electrode, creative to have obtained a kind of ternary or four The presoma of first positive electrode forms spheric granules by six square pieces, and is also compounded with receiving for presoma in six square piece of presoma Rice grain, the secondary spherical particle of the nano particle composition of the hexagonal flake and its surface of these multilayers, structural integrity is uniform, The nano particle on hexagonal flake surface can be effectively improved positive electrode processing performance, improve cathode material structure stability, Positive electrode cycle performance is improved, while the nano particle on hexagonal flake surface increases the specific surface area of material, reduces Internal resistance during material circulation improves the high rate performance of material.And preparation method simple process, mild condition are applicable in In large-scale production and application.
Similar structures before especially comparing contain the positive electrode material precursor of colloidal solid material, provided by the invention It is the positive electrode material precursor of same material, and nano particle can be embedded in and be filled between the lamella of layered body, material It is uniform, there is better structural stability, improve cycle performance.And insertion and filling more increase the specific surface of material Product, reduces the interface internal resistance in cyclic process, improves the high rate performance of positive electrode.
The experimental results showed that the anode material for lithium-ion batteries that system of the present invention is obtained has the same of excellent processing performance When have both good cycle performance and high rate performance, 0.1C discharge capacity is 194mAh/g, and 5C discharge capacity is 162mAh/g, 60 circle capacity retention ratios are 95%.
Detailed description of the invention
Fig. 1 is the SEM scanning electron microscope (SEM) photograph under 5 μm of scales of nickel-cobalt-manganese ternary material precursor prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph under 1 μm of scale of nickel-cobalt-manganese ternary material precursor prepared by the embodiment of the present invention 1；
Fig. 3 is the SEM scanning electron microscope (SEM) photograph of nickel-cobalt-manganternary ternary anode material prepared by the embodiment of the present invention 1；
Fig. 4 is the SEM scanning electron microscope (SEM) photograph of nickel-cobalt-manganternary ternary anode material prepared by the embodiment of the present invention 1；
Fig. 5 is the ternary precursor schematic diagram of preparation of the embodiment of the present invention；
Fig. 6 is the chemical property figure of nickel-cobalt-manganternary ternary anode material prepared by the embodiment of the present invention 1.
Specific embodiment
In order to further appreciate that the present invention, below in conjunction with the embodiment of the present invention, technical solution of the present invention is carried out clear Chu is fully described by, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments. Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts all Other embodiments shall fall within the protection scope of the present invention.
The present invention provides a kind of positive electrode material precursors, have the general formula as shown in formula (I):
NixCoyMnzAl1-x-y-z(OH)2(I)；
Wherein, 0 < x < 1,0 < y < 1, x+y < 1,0≤z < 1, x+y+z≤1；
The spheric granules that the positive electrode material precursor forms for six square piece of positive electrode material precursor, and the positive electrode Positive electrode material precursor nano particle is compounded in six square piece of presoma.
The positive electrode is not particularly limited in the present invention, with conventional cathode material well known to those skilled in the art Definition, those skilled in the art can select and adjust according to applicable cases, properties of product and quality requirement, this The presoma that the positive electrode material precursor preferably includes tertiary cathode material and/or quaternary positive electrode is invented, more preferably The presoma of tertiary cathode material or quaternary positive electrode, more preferably nickle cobalt lithium manganate tertiary cathode material (NCM), nickel cobalt aluminium The presoma of sour lithium tertiary cathode material (NCA) or nickel cobalt manganese lithium aluminate quaternary positive electrode (NCMA).
The definition of the presoma is not particularly limited in the present invention, with conventional cathode material well known to those skilled in the art The definition of material precursor, those skilled in the art can select according to applicable cases, properties of product and quality requirement It selects and adjusts, positive electrode material precursor of the present invention is preferably the hydroxide precursor of positive electrode.It has such as formula (I) Shown in general formula:
NixCoyMnzAl1-x-y-z(OH)2(I)；Wherein, 0 < x < 1,0 < y < 1, x+y < 1,0≤z < 1, x+y+z≤1.
In the present invention, as z=0, formula (I) is the logical of nickel cobalt lithium aluminate tertiary cathode material hydroxide precursor Formula；As x+y+z=1, formula (I) is the general formula of nickle cobalt lithium manganate tertiary cathode material hydroxide precursor；As z ≠ 0 and x+y When+z ≠ 1, formula (I) is the general formula of nickel cobalt manganese lithium aluminate quaternary positive electrode hydroxide precursor.In the present invention, work as x+y+ When z=1, z ≠ 0, i.e. x+y < 1.
Positive electrode material precursor of the present invention be six square piece of positive electrode material precursor composition spheric granules, and it is described just Positive electrode material precursor nano particle is compounded in six square piece of pole material precursor.Positive electrode material precursor provided by the invention It is positive electrode material precursor material in structure.
The present invention is not special to the building form of six square piece of presoma composition spheric granules (or spherical particle) Limitation, with conventional building form well known to those skilled in the art, those skilled in the art can be according to applicable cases, production Moral character energy and quality requirement are selected and are adjusted, and composition of the present invention, which preferably stacks, to be formed；The six of the presoma Square piece can be self-assembled into layered body with multi-disc, and layered body stacks to form spheric granules again, wherein can also be mingled with six square piece of single layer. Six square pieces of positive electrode material precursor i.e. of the present invention preferably include the layered body of six square piece of multilayer composition, or, six side of multilayer Six square piece of layered body and single layer of piece composition.
The number of plies of multilayer of the present invention is not particularly limited, with the conventional number of plies well known to those skilled in the art, Those skilled in the art can select and adjust according to applicable cases, properties of product and quality requirement, of the present invention The number of plies of multilayer is preferably 2~50 layers, more preferably 12~40 layers, more preferably 22~30 layers.
To six square piece of multilayer, i.e. the thickness of layered body is not particularly limited the present invention, ripe with those skilled in the art The conventional number of plies thickness known, those skilled in the art can carry out according to applicable cases, properties of product and quality requirement Selection and adjustment, the thickness of six square piece of multilayer of the present invention is preferably 50~200nm, more preferably 75~175nm, more preferably For 100~150nm, it is specifically as follows 80~150nm.
There is gap, more particularly, knot of the present invention in single layered body between the layered body of stacking of the present invention On structure, there is gap between each lamella, the piece interlayer of six square piece of multilayer of the present invention has gap.It is of the present invention just Gap of the pole material precursor nano-particles reinforcement between the layered body of the stacking, while being also compounded in six side of multilayer The surface of piece, and the piece lamellar spacing of single layered body.
The compound mode is not particularly limited in the present invention, is with composite definitions well known to those skilled in the art Can, the present invention is preferably deposition, growth, filling, cladding, modifies, is laminated or generates, and more preferably deposits, grows or fills, most It preferably deposits or fills.
The ratio of six square piece and nano particle is not particularly limited in the present invention, with well known to those skilled in the art Conventional ratio, those skilled in the art can select according to practical condition, product situation and properties of product, The mass ratio of six square piece of positive electrode material precursor of the present invention and the positive electrode material precursor nano particle is preferably 10:(1 ~5), more preferably 10:(1.5~4.5), more preferably 10:(2~4), more preferably 10:(2.5~3.5).
The partial size of the nano particle is not particularly limited in the present invention, with conventional nano well known to those skilled in the art The partial size of particle, those skilled in the art can be selected according to applicable cases, properties of product and quality requirement and Adjustment, the partial size of nano particle of the present invention is preferably 100~300nm, more preferably 120~280nm, more preferably 150 ~250nm, more preferably 180~230nm.The shape of the nano particle is not particularly limited in the present invention, with this field skill The shape of conventional nano particle known to art personnel, those skilled in the art can according to applicable cases, properties of product with And quality requirement is selected and is adjusted, nano particle of the present invention is preferably irregular shape nano particle, can be ball Shape, cube shape or the polygon bodily form.
The partial size of the spheric granules is not particularly limited in the present invention, with conventional cathode well known to those skilled in the art The partial size of material precursor, those skilled in the art can carry out according to applicable cases, properties of product and quality requirement Selection and adjustment, the partial size of spheric granules of the present invention is preferably 5~15 μm, and more preferably 7~13 μm, more preferably 9~ 11μm。
Above-mentioned steps of the present invention provide a kind of positive electrode material precursor, and there is hexagonal flake to stack to form primary particle (layered body), and between the layer of layered body have gap, nano particle can be deposited on again layered body sheet surfaces and In gap, several layered bodies and six square piece of single layer stack to form precursor of lithium ionic cell positive material of the present invention again.It is special It is not the positive electrode material precursor that the similar structures before comparing contain colloidal solid material, the present invention is to provide same materials Positive electrode material precursor, and nano particle can be embedded in and be filled between the lamella of layered body, and material is uniform, have more Good structural stability, improves cycle performance.And insertion and filling more increase the specific surface area of material, reduce and follow Interface internal resistance during ring, improves the high rate performance of positive electrode.
The present invention provides a kind of preparation methods of positive electrode material precursor, comprising the following steps:
1) after mixing nickel salt, manganese salt and/or aluminium salt, cobalt salt and water, mixed liquor is obtained；
2) mixed liquor, complexing agent and alkali is added, after being reacted, obtains the first mixed solution；
3) into the first mixed solution that above-mentioned steps obtain, mixed liquor, complexing agent and alkali, then secondary response are continuously added Afterwards, the second mixed solution is obtained；
4) the second mixed solution for obtaining above-mentioned steps obtains positive electrode material precursor after ageing.
The present invention is to the selection of material, ratio and its corresponding optimum principle in the preparation method, such as without especially note It is bright, it is preferably consistent with the selection of material, ratio in aforementioned positive electrode material precursor, and its corresponding optimum principle, herein not It repeats one by one again.
After the present invention first mixes nickel salt, manganese salt and/or aluminium salt, cobalt salt and water, mixed liquor is obtained.
The additional proportion of the water is not particularly limited in the present invention, with the ratio of solvent well known to those skilled in the art , those skilled in the art can select and adjust according to the condition of production, properties of product and quality requirement, of the invention In the mixed liquor, the total mol concentration of the manganese salt and/or aluminium salt, nickel salt and cobalt salt is preferably 1~3.5mol/L, more preferably For 1.5~3mol/L, more preferably 2~2.5mol/L.
The specific choice between the nickel salt, manganese salt and/or aluminium salt, cobalt salt is not particularly limited in the present invention, with ability Conventional salt known to field technique personnel, those skilled in the art can be according to the condition of production, properties of product and quality It is required that selected and adjusted, nickel salt of the present invention be preferably one of nickel sulfate, nickel nitrate, nickel oxalate and nickel chloride or It is a variety of；The cobalt salt is preferably one of cobaltous sulfate, cobalt nitrate, cobalt oxalate and cobalt chloride or a variety of；The manganese salt is preferably One of manganese sulfate, manganese nitrate, manganese oxalate and manganese chloride are a variety of；The aluminium salt is preferably aluminum sulfate, aluminum nitrate, oxalic acid aluminium With one of aluminium chloride or a variety of.
The ratio between the nickel salt, manganese salt and/or aluminium salt, cobalt salt is not particularly limited in the present invention, with this field skill The ratio of conventional three-way known to art personnel or quaternary positive electrode, those skilled in the art can according to the condition of production, Properties of product and quality requirement are selected and are adjusted, nickel salt, manganese salt and/or aluminium salt of the present invention, the molar ratio of cobalt salt Preferably x:(1-x-y): y, wherein the molar ratio of manganese salt and aluminium salt is preferably z:(1-x-y-z).
The mixed mode and step is not particularly limited in the present invention, with mixing well known to those skilled in the art Mode and step, those skilled in the art can be selected according to the condition of production, properties of product and quality requirement and Adjustment, mixing of the present invention are preferably stirred.The present invention is to improve mixed effect, guarantees the performance of final product, The mixed specific steps can be, when precursor is ternary anode material precursor or quaternary positive electrode material precursor, It is preferred that using above-mentioned mixing step；When precursor is quaternary positive electrode material precursor, following mixing steps are more preferably used:
After nickel salt, manganese salt, cobalt salt and water are mixed, just mixed liquor is obtained；
After aluminium salt and water are mixed, aluminum salt solution is obtained；
After first mixed liquor and aluminum salt solution are mixed, mixed liquor is obtained.
The concentration of the aluminum salt solution is not particularly limited in the present invention, with normal concentration well known to those skilled in the art , those skilled in the art can select and adjust according to the condition of production, properties of product and quality requirement, of the invention The molar concentration of the aluminum salt solution is preferably 0.1~2mol/L, more preferably 0.4~1.6mol/L, more preferably 0.8~ 1.2mol/L。
Mixed liquor, complexing agent and alkali is then added in the present invention, after being reacted, obtains the first mixed solution, i.e., to reaction Mixed liquor, complexing agent and alkali are added in container, after being reacted, obtains the first mixed solution.Mixed liquor of the present invention is upper State the mixed liquor that step obtains.
The selection of the complexing agent is not particularly limited in the present invention, with such reaction well known to those skilled in the art Conventional complexing agent, those skilled in the art can be selected according to the condition of production, properties of product and quality requirement and Adjustment, complexing agent of the present invention are preferably selected from ammonium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, ammonium phosphate, diammonium hydrogen phosphate, biphosphate One of ammonium, ammonium nitrate and urea are a variety of, more preferably ammonium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, ammonium phosphate, diammonium hydrogen phosphate, Ammonium dihydrogen phosphate, ammonium nitrate or urea, most preferably ammonium hydroxide.
The dosage of the complexing agent is not particularly limited in the present invention, with such reaction well known to those skilled in the art Conventional amount of complex, those skilled in the art can select according to the condition of production, properties of product and quality requirement It selects and adjusts, in step 2) of the present invention, the molal quantity of the complexing agent and the nickel salt, manganese salt and/or aluminium salt, cobalt salt The ratio of total mole number is preferably (1~10): 1, more preferably (3~8): 1, more preferably (5~6): 1.
The present invention is to improve the pattern of final products, and complete and refinement preparation process, the complexing agent are more preferably complexed Agent solution, the concentration of the enveloping agent solution are preferably 0.1~3mol/L, more preferably 0.5~2.5mol/L, more preferably 1 ~2mol/L.
The selection of the alkali is not particularly limited in the present invention, with alkali well known to those skilled in the art, this field Technical staff can select and adjust according to the condition of production, properties of product and quality requirement, and alkali of the present invention is preferred Selected from one of lithium hydroxide, sodium hydroxide and potassium hydroxide or a variety of, more preferably lithium hydroxide, sodium hydroxide or hydrogen-oxygen Change potassium, most preferably sodium hydroxide.
The dosage of the alkali is not particularly limited in the present invention, and those skilled in the art can be according to the condition of production, product Performance and quality requirement are selected and are adjusted, and the present invention uses alkali as precipitating reagent, by adjusting the first mixed solution PH value firstly generates multilayer hexagonal flake positive electrode material precursor.In step 2) of the present invention, first mixed solution The pH value of pH value, i.e., the described reaction is preferably 7.5~12.0, and more preferably 8.5~11.0, more preferably 9.5~10.0.
The present invention is to improve the pattern of final products, and complete and refinement preparation process, the alkali (precipitating reagent) is more preferably Lye, the concentration of the lye are preferably 1.5~6.5mol/L, more preferably 2.5~5.5mol/L, more preferably 3.5~ 4.5mol/L。
The other conditions of the reaction are not particularly limited in the present invention, with such reaction well known to those skilled in the art Condition, those skilled in the art can select and adjust according to the condition of production, properties of product and quality requirement, The present invention guarantees and the pattern of regulation final products, and complete and refinement preparation process, the time of the reaction is preferably 4~36h, More preferably 10~30h, more preferably 15~25h.The temperature of reaction of the present invention is preferably 40~70 DEG C, more preferably 45 ~65 DEG C, more preferably 50~60 DEG C.
The mode of the addition is not particularly limited in the present invention, is with adding manner well known to those skilled in the art Can, those skilled in the art can select and adjust according to the condition of production, properties of product and quality requirement, and the present invention is The pattern of final products, complete and optimizing process are improved, the addition is preferably slowly added to or is added dropwise.The present invention is to institute It states the speed for being slowly added to or being added dropwise to be not particularly limited, with the speed well known to those skilled in the art for being slowly added to or being added dropwise , those skilled in the art can select and adjust according to the condition of production, properties of product and quality requirement.
The present invention is stated then up in the first mixed solution that step obtains, and continuously adds mixed liquor, complexing agent and alkali, then After secondary response, the second mixed solution is obtained.Continuously added into the reaction system that above-mentioned steps obtain mixed liquor, complexing agent and After alkali, then secondary response, the second mixed solution is obtained.Mixed liquor of the present invention is the mixed liquor that step 1) obtains.
The selection of the complexing agent of above-mentioned steps is not particularly limited in the present invention, with well known to those skilled in the art such The conventional complexing agent of reaction, those skilled in the art can carry out according to the condition of production, properties of product and quality requirement Selection and adjustment, complexing agent of the present invention are preferably selected from ammonium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, ammonium phosphate, diammonium hydrogen phosphate, phosphorus One of acid dihydride ammonium, ammonium nitrate and urea are a variety of, more preferably ammonium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, ammonium phosphate, phosphoric acid Hydrogen diammonium, ammonium dihydrogen phosphate, ammonium nitrate or urea, most preferably ammonium hydroxide.
The dosage of the complexing agent of above-mentioned steps is not particularly limited in the present invention, with well known to those skilled in the art such The conventional amount of complex of reaction, those skilled in the art can be according to the condition of production, properties of product and quality requirements It is selected and is adjusted, in step 3) of the present invention, the molal quantity of the complexing agent and the nickel salt, manganese salt and/or aluminium salt, The ratio of the total mole number of cobalt salt is preferably (5~20): 1, more preferably (7~18): 1, more preferably (10~15): 1.
The present invention is to improve the pattern of final products, and complete and refinement preparation process, the complexing agent of the above-mentioned steps is more Preferably enveloping agent solution, the concentration of the enveloping agent solution of the above-mentioned steps are preferably 0.1~3mol/L, and more preferably 0.5 ~2.5mol/L, more preferably 1~2mol/L.
The selection of the alkali of above-mentioned steps is not particularly limited in the present invention, with alkali well known to those skilled in the art, Those skilled in the art can select and adjust according to the condition of production, properties of product and quality requirement, of the present invention Alkali is preferably selected from one of lithium hydroxide, sodium hydroxide and potassium hydroxide or a variety of, more preferably lithium hydroxide, sodium hydroxide Or potassium hydroxide, most preferably sodium hydroxide.
The dosage of the alkali of the above-mentioned steps is not particularly limited in the present invention, and those skilled in the art can be according to production Situation, properties of product and quality requirement are selected and are adjusted, and the present invention, as precipitating reagent, is mixed using alkali by regulation second Close solution pH value so that above-mentioned steps 2) in multilayer hexagonal flake nickel cobalt manganese aluminum salt hydroxide presoma on, growth Granular nickel cobalt manganese aluminum salt hydroxide presoma.In step 3) of the present invention, the pH value of second mixed solution, i.e. institute The pH value for stating again secondary response is preferably 9.5~13.0, and more preferably 10~12.5, more preferably 10.5~12.0, more preferably 11.0~11.5.
The present invention is to further increase the effect of regulation, guarantees the pattern of final products, and the pH value of the secondary response again is excellent Choosing is higher than the pH value of the reaction by 0.25~2, and more preferably 0.5~1.7, more preferably 0.7~1.5, more preferably 1~1.2.
The present invention is to improve the pattern of final products, complete and refinement preparation process, the alkali (precipitating of the above-mentioned steps Agent) it is more preferably lye, the concentration of the lye of the above-mentioned steps is preferably 1.5~6.5mol/L, more preferably 2.5~ 5.5mol/L, more preferably 3.5~4.5mol/L.
The other conditions of the secondary response again are not particularly limited in the present invention, with well known to those skilled in the art such The condition of reaction, those skilled in the art can be selected according to the condition of production, properties of product and quality requirement and Adjustment, the present invention guarantees and the pattern of regulation final products, and complete and refinement preparation process, the time of the secondary response again are preferred For 36~50h, more preferably 40~47h, more preferably 42~45h.The temperature of secondary response again of the present invention is preferably 45~ 65 DEG C, more preferably 48~62 DEG C, more preferably 50~60 DEG C.
The mode continuously added is not particularly limited in the present invention, with adding manner well known to those skilled in the art , those skilled in the art can select and adjust according to the condition of production, properties of product and quality requirement, of the invention For the pattern for improving final products, complete and optimizing process, described continuously add preferably are slowly added to or are added dropwise.This hair It is bright that the speed for being slowly added to or being added dropwise is not particularly limited, it is slowly added to or is added dropwise with well known to those skilled in the art Speed, those skilled in the art can select and adjust according to the condition of production, properties of product and quality requirement.
The second mixed solution that the present invention finally obtains above-mentioned steps obtains positive electrode material precursor after ageing.
The mode and condition of the ageing is not particularly limited in the present invention, with ageing well known to those skilled in the art Mode and condition, those skilled in the art can be selected according to the condition of production, properties of product and quality requirement and Adjustment, the time of ageing of the present invention is preferably 20~40h, more preferably 23~38h, more preferably 25~35h, more preferably For 27~32h.
The present invention is to improve the quality of final products, and optimization and complete process flow, it is also preferable to include rear after the ageing Processing step.Post-processing of the present invention preferably includes one of washing, dehydration and drying or a variety of, more preferably multiple water It washes, be repeatedly dehydrated and dry, more preferably successively repeatedly washed and be dehydrated, finally dried.
The above-mentioned improved coprecipitation reaction of the present invention, may be summarized to be 3 steps:
Firstly, generating multilayer hexagonal flake positive electrode hydroxide precursor；
Then, by regulation so that the growth of above-mentioned multilayer hexagonal flake positive electrode hydroxide precursor is granular just Pole material hydroxide presoma；
Finally, ageing obtains uniform multilayer hexagonal flake and the compound positive electrode hydroxide precursor of graininess.
The present invention is that complete and optimizing process, above-mentioned preparation step can be specific when preparing quaternary positive electrode For following steps:
Nickel salt, cobalt salt and manganese salt are mixed, mixed solution is obtained, this is the first mixing salt solution.The mixed solution The total concentration of middle nickel salt, cobalt salt and manganese salt is 1~3.5mol/L.
Second of salting liquid i.e. aluminum salt solution is configured, institute's aluminum salt solution concentration is 0.1~2mol/L；
By the first mixed solution, second of salting liquid, the sodium hydroxide solution and concentration that concentration is 1.5~6.5mol/L It is mixed for the ammonia spirit of 0.1~3mol/L, obtains second of mixed solution, the flow for adjusting sodium hydroxide solution makes second The pH of mixed solution is 7.5~12.0.It is continuously available after second of solution reaction with to lead to six square piece of multilayer that formula (I) indicates The positive electrode hydroxide precursor of the spheric granules of shape composition.
Continue by the first mixed solution, second of salting liquid, concentration be 1.5~6.5mol/L sodium hydroxide solution with Concentration be 0.1~3mol/L ammonia spirit mix, adjust sodium hydroxide solution flow make the pH 9.5 of the mixed solution~ It is continuously available to have behind 13.0, then secondary response and graininess positive electrode hydroxide precursor is indicated with logical formula (I)；Continue to be aged Obtain the uniform multilayer hexagonal flake positive electrode hydroxide precursor and graininess positive electrode hydrogen-oxygen that logical formula (I) indicates The positive electrode hydroxide precursor of compound forerunner's bluk recombination.
Above-mentioned steps of the present invention provide the preparation method of positive electrode material precursor its step, according to centainly rubbing The nickel salt (a) of your ratio: cobalt salt (b): manganese salt/aluminium salt (c), wherein (a is preferably 4~8, and more preferably 5~7, more preferably 5.5 ~6.5；B is preferably 1~3, and more preferably 1.3~2.7, more preferably 1.5~2.5；C is preferably 1~9, and more preferably 3~7, More preferably 4~6) nickel cobalt manganese, the salting liquid of three kinds of materials of aluminium, configuration and the precipitating of above-mentioned salting liquid same molar ratio are configured Agent solution and certain density enveloping agent solution, above-mentioned three kinds of solution is added dropwise in reaction kettle according to given pace respectively forms one The specific reaction system of kind, while the phase by control pH, temperature and time, makes it generate nanosphere particle and obtains after the reaction Spheric granules is formed by six square piece of multilayer, and in six square pieces and gap, deposits the hydroxide precursor of spherical nanoparticle.This Invention preparation method simple process, granular precursor size tunable is uniform, regular appearance, and tap density is high, and six square piece layers it Between there are certain gaps, thus follow-up sintering procedure structure keep preferably be conducive to lithium ion spread.The system that the present invention improves Standby technique, positive electrode material precursor obtained, regular appearance, component is uniform, and tap density is high, and it is raw to be suitable for industrial mass It produces.
The present invention provides a kind of positive electrodes, have the general formula as shown in formula (II):
Li1+wNixCoyMnzAl1-x-y-zO2(II),
Wherein, 0 < x < 1,0 < y < 1, x+y < 1,0≤z < 1, x+y+z≤1, -0.5≤w≤0.5；
The positive electrode is the spheric granules of six square piece of positive electrode composition, and compound in six square piece of the positive electrode There is positive electrode nano particle.
The present invention is to the selection of material, ratio and its corresponding optimum principle in the positive electrode, such as without especially note It is bright, it is preferred with the selection of material, ratio in aforementioned positive electrode material precursor and preparation method thereof, and its corresponding optimum principle Unanimously, this is no longer going to repeat them.
The molal quantity of Li of the present invention, i.e. 1+w are preferably -1.5~1.5, more preferably -1.3~1.3, more preferably - 1.1~1.1, most preferably 1.
The positive electrode of the present invention preferably positive electrode material precursor as described in above-mentioned technical proposal any one or on Positive electrode material precursor prepared by preparation method described in technical solution any one is stated, is after heat treatment obtained with lithium salts. The temperature of heat treatment of the present invention is preferably 725 DEG C~1150 DEG C, more preferably 850 DEG C~1050 DEG C, more preferably 900 DEG C ~1000 DEG C.
The present invention is to the building form of six square piece of positive electrode composition spheric granules (or spherical particle) without spy Do not limit, with conventional building form well known to those skilled in the art, those skilled in the art can according to applicable cases, Properties of product and quality requirement are selected and are adjusted, and composition of the present invention, which preferably stacks, to be formed；The positive electrode Six square pieces layered body can be self-assembled into multi-disc, layered body stacks to form spheric granules again, wherein can also be mingled with single layer six Square piece.Six square pieces of positive electrode i.e. of the present invention preferably include the layered body of six square piece of multilayer composition, or, six square piece of multilayer Six square piece of layered body and single layer of composition.
The number of plies of multilayer of the present invention is not particularly limited, with the conventional number of plies well known to those skilled in the art, Those skilled in the art can select and adjust according to applicable cases, properties of product and quality requirement, of the present invention The number of plies of multilayer is preferably 2~50 layers, more preferably 12~40 layers, more preferably 22~30 layers.
To six square piece of multilayer, i.e. the thickness of layered body is not particularly limited the present invention, ripe with those skilled in the art The conventional number of plies thickness known, those skilled in the art can carry out according to applicable cases, properties of product and quality requirement Selection and adjustment, the thickness of six square piece of multilayer of the present invention is preferably 100~300nm, and more preferably 150~250nm is more excellent It is selected as 180~230nm.
There is gap, more particularly, knot of the present invention in single layered body between the layered body of stacking of the present invention On structure, there is gap between each lamella, the piece interlayer of six square piece of multilayer of the present invention has gap.It is of the present invention just Pole material nanoparticle is compounded in the gap between the layered body of the stacking, while being also compounded in the table of six square piece of multilayer Face, and the piece lamellar spacing of single layered body.
The compound mode is not particularly limited in the present invention, is with composite definitions well known to those skilled in the art Can, the present invention is preferably deposition, growth, filling, cladding, modifies, is laminated or generates, and more preferably deposits, grows or fills, most It preferably deposits or fills.
The ratio of six square piece and nano particle is not particularly limited in the present invention, with well known to those skilled in the art Conventional ratio, those skilled in the art can select according to practical condition, product situation and properties of product, The mass ratio of six square piece of positive electrode of the present invention and the positive electrode nano particle is preferably 10:(1~5), more preferably For 10:(1.5~4.5), more preferably 10:(2~4), more preferably 10:(2.5~3.5).
The partial size of the nano particle is not particularly limited in the present invention, with conventional nano well known to those skilled in the art The partial size of particle, those skilled in the art can be selected according to applicable cases, properties of product and quality requirement and Adjustment, the partial size of nano particle of the present invention is preferably 100~300nm, more preferably 120~280nm, more preferably 150 ~250nm, more preferably 180~230nm.The shape of the nano particle is not particularly limited in the present invention, with this field skill The shape of conventional nano particle known to art personnel, those skilled in the art can according to applicable cases, properties of product with And quality requirement is selected and is adjusted, nano particle of the present invention is preferably irregular shape nano particle, can be ball Shape, cube shape or the polygon bodily form.
The partial size of the spheric granules is not particularly limited in the present invention, with conventional cathode well known to those skilled in the art The partial size of material precursor, those skilled in the art can carry out according to applicable cases, properties of product and quality requirement Selection and adjustment, the partial size of spheric granules of the present invention is preferably 5~15 μm, and more preferably 7~13 μm, more preferably 9~ 11μm。
Above-mentioned steps of the present invention provide a kind of positive electrode, and there is hexagonal flake to stack to form primary particle (multilayer Body), and there is gap between the layer of layered body, nano particle can be deposited in the sheet surfaces and gap of layered body again, Several layered bodies and six square piece of single layer stack to form anode material for lithium-ion batteries of the present invention again.
The positive electrode material precursor that abovementioned steps obtain is mixed heat treatment by the present invention with lithium salts again, the multilayer in presoma The secondary spherical particle structure of hexagonal flake and its surface spheric granules composition is intact, and the spherical shape on hexagonal flake surface Particle can be effectively improved positive electrode processing performance, improve cathode material structure stability, improve positive electrode circulation Performance, while the spheric granules on hexagonal flake surface increases the specific surface area of material reduces interior during material circulation Resistance, improves the high rate performance of material.
The present invention also provides a kind of lithium ion batteries, including positive electrode described in above-mentioned technical proposal any one.
The structure of the lithium ion battery is not particularly limited in the present invention, with conventional lithium well known to those skilled in the art The structure of ion battery, those skilled in the art can select according to applicable cases, properties of product and quality requirement It selects and adjusts, lithium ion battery of the present invention preferably includes anode, cathode, diaphragm and electrolyte.The anode preferably includes Positive electrode active materials, conductive agent, binder, solvent and collector etc..Wherein, the positive electrode active materials are preferably above-mentioned ternary Positive electrode or quaternary positive electrode.
Above-mentioned steps of the present invention provide a kind of positive electrode material precursor and preparation method thereof, positive electrode and lithium-ion electric Pond.The present invention starts with from the presoma of positive electrode, a kind of creative presoma for having obtained ternary or quaternary positive electrode, Spheric granules is formed by six square pieces, and is also compounded with the nanometer of presoma in six square piece of presoma and six square piece lamellar spacings Grain, the secondary spherical particle of the nano particle composition of the hexagonal flake and its surface of these multilayers, structural integrity is uniform, six sides The nano particle of schistose surface can be effectively improved positive electrode processing performance, improve cathode material structure stability, improve Positive electrode cycle performance, while the nano particle on hexagonal flake surface increases the specific surface area of material, reduce material Internal resistance in cyclic process improves the high rate performance of material.And preparation method simple process, mild condition, it is suitable for big Large-scale production application
The experimental results showed that the anode material for lithium-ion batteries that system of the present invention is obtained has the same of excellent processing performance When have both good cycle performance and high rate performance, 0.1C discharge capacity is 194mAh/g, and 5C discharge capacity is 162mAh/g, 60 circle capacity retention ratios are 95%.
In order to further illustrate the present invention, with reference to embodiments to a kind of positive electrode material precursor provided by the invention and Preparation method, positive electrode and lithium ion battery are described in detail, but it is to be understood that these embodiments are with this hair Implemented under premised on bright technical solution, the detailed implementation method and specific operation process are given, is only further Illustrate the features and advantages of the present invention, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to Following embodiments.
Raw material in following embodiment is commercial product.
Embodiment 1
(1) weighing nickel sulfate, cobaltous sulfate and manganese sulfate respectively is 21.56kg, 2.8kg and 13.5kg, according to chemical molecular Formula LiNi0.82Co0.1Mn0.08O2In mole specific concentration stirring be dissolved in deionized water, be configured to the mixing salt solution of 2mol/L；
(2) 35.6kg sodium hydroxide is weighed, for stirring and dissolving in deionized water, the sodium hydroxide for being configured to 8mol/L is molten Liquid is used as precipitating reagent；
(3) 3400ml ammonium hydroxide is measured, is diluted with deionized water, and be configured to the ammonia spirit of 2mol/L, as complexing agent It uses；
(4) constant temperature water bath in reaction kettle is heated to 55 DEG C with the mode of direct electro heating, it is configured by above-mentioned 3 kinds Solution is slowly added dropwise respectively to reaction kettle, and controlling reaction kettle pH value is 11.3, reacts 35h.
(5) continue to be slowly added dropwise to reaction kettle, adjust ammonium hydroxide flow and hydrogen-oxygen above-mentioned 3 kinds of configured solution respectively Changing sodium flow stablizes pH after 12.3, reaction 40h；It is aged after 40h that obtain multilayer hexagonal flake compound with graininess again Nickel cobalt manganese hydroxide precursor.
(6) above-mentioned coprecipitated product is repeatedly washed, nickel-cobalt-manganese ternary material precursor obtained after being dehydrated, drying Particle.
The nickel-cobalt-manganese ternary material precursor particle prepared to the embodiment of the present invention 1 characterizes.
Referring to Fig. 1, Fig. 1 is that the SEM under 5 μm of scales of nickel-cobalt-manganese ternary material precursor prepared by the embodiment of the present invention 1 is swept Retouch electron microscope.
Referring to fig. 2, Fig. 2 is that the SEM under 1 μm of scale of nickel-cobalt-manganese ternary material precursor prepared by the embodiment of the present invention 1 is swept Retouch electron microscope.
By Fig. 1 and Fig. 2 it is found that granular precursor particle diameter distribution, regular appearance, six square piece multi-disc of positive electrode material precursor is certainly It is assembled into layered body, layered body stacks to form spheric granules again, and the nanometer of positive electrode material precursor is deposited in six square pieces Grain.There is gap between the layered body of stacking, and there is gap, nanoparticle deposition between each lamella of single layered body Gap between the layered body of stacking, while it also being deposited upon the surface of six square piece of multilayer, and the piece interlayer of single layered body Gap.
The nickel-cobalt-manganese ternary material precursor prepared to the embodiment of the present invention 1 detects, the results showed that, tap density is 2.7g/ml, D50 are 8 μm.
The modifications such as undoped and cladding are obtained after above-mentioned granular precursor is mixed with lithium carbonate, after high-temperature calcination Positive electrode LiNi0.82Co0.1Mn0.08O2, it is assembled into the half-cell for not carrying out any other modification, carries out chemical property survey Examination.
It is the SEM scanning electron microscope (SEM) photograph of nickel-cobalt-manganternary ternary anode material prepared by the embodiment of the present invention 1 referring to Fig. 3, Fig. 3.
From the figure 3, it may be seen that six square piece multi-disc of positive electrode is self-assembled into layered body, layered body stacks to form spheric granules again, And six are deposited with positive electrode nano particle in square piece.There is gap, and single layered body is each between the layered body of stacking There is gap, gap of the nanoparticle deposition between the layered body of stacking between a lamella, while also being deposited upon six side of multilayer The surface of piece, and the piece lamellar spacing of single layered body.
Performance test results show that 0.1C discharge capacity is 194mAh/g；0.2C capacity 190；0.5C capacity is 185mAh/ g；1C capacity is 182mAh/g；5C discharge capacity is 162mAh/g.Its 60 circle capacity retention ratio is 95%.
Embodiment 2
(1) weighing nickel sulfate, cobaltous sulfate and manganese sulfate respectively is 15.77kg, 5.63kg and 3.38kg, according to chemical molecular Formula LiNi0.6Co0.2Mn0.2O2In mole specific concentration stirring be dissolved in deionized water, be configured to the mixing salt solution of 2mol/L；
(2) 17.8kg sodium hydroxide is weighed, for stirring and dissolving in deionized water, the sodium hydroxide for being configured to 4mol/L is molten Liquid is used as precipitating reagent；
(3) 3400ml ammonium hydroxide is measured, is diluted with deionized water, and be configured to the ammonia spirit of 2mol/L, as complexing agent It uses；
(4) constant temperature water bath in reaction kettle is heated to 55 DEG C with the mode of direct electro heating, it is configured by above-mentioned 3 kinds Solution is slowly added dropwise respectively to reaction kettle, and controlling reaction kettle pH value is 11.25, reacts 30h.
(5) continue to be slowly added dropwise to reaction kettle, adjust ammonium hydroxide flow and hydrogen-oxygen above-mentioned 3 kinds of configured solution respectively Changing sodium flow stablizes pH after 11.78, reaction 40h；It is aged after 20h that obtain multilayer hexagonal flake compound with graininess again Nickel cobalt manganese hydroxide precursor.
(6) above-mentioned coprecipitated product is repeatedly washed, nickel-cobalt-manganese ternary material precursor obtained after being dehydrated, drying Particle.
The nickel-cobalt-manganese ternary material precursor prepared to the embodiment of the present invention 2 detects, the results showed that, tap density is 2.4g/ml, D50 are 10 μm.
The modifications such as undoped and cladding are obtained after above-mentioned granular precursor is mixed with lithium carbonate, after high-temperature calcination Positive electrode LiNi0.6Co0.2Mn0.2O2, it is assembled into half-cell and carries out electrochemical property test.
Embodiment 3
(1) weighing nickel sulfate, cobaltous sulfate and manganese sulfate respectively is 13.14kg, 56.23kg and 50.70kg, according to chemistry point Minor LiNi0.5Co0.2Mn0.3O2In mole specific concentration stirring be dissolved in deionized water, the salt-mixture for being configured to 2mol/L is molten Liquid；
(2) 8.9kg sodium hydroxide is weighed, stirring and dissolving is configured to the sodium hydroxide solution of 2mol/L in deionized water, It is used as precipitating reagent；
(3) 1700ml ammonium hydroxide is measured, is diluted with deionized water, and be configured to the ammonia spirit of 1mol/L, as complexing agent It uses；
(4) constant temperature water bath in reaction kettle is heated to 60 DEG C with the mode of direct electro heating, it is configured by above-mentioned 3 kinds Solution is slowly added dropwise respectively to reaction kettle, and controlling reaction kettle pH value is 10.5, reacts 30h.
(5) continue to be slowly added dropwise to reaction kettle, adjust ammonium hydroxide flow and hydrogen-oxygen above-mentioned 3 kinds of configured solution respectively Changing sodium flow stablizes pH after 11.3, reaction 40h；It is aged after 30h that obtain multilayer hexagonal flake compound with graininess again Nickel cobalt manganese hydroxide precursor.
(6) above-mentioned coprecipitated product is repeatedly washed, nickel-cobalt-manganese ternary material precursor obtained after being dehydrated, drying Particle.
The nickel-cobalt-manganese ternary material precursor prepared to the embodiment of the present invention 3 detects, the results showed that, tap density is 2.1g/ml, D50 are 12 μm.
The modifications such as undoped and cladding are obtained after above-mentioned granular precursor is mixed with lithium carbonate, after high-temperature calcination Positive electrode LiNi0.5Co0.2Mn0.3O2, it is assembled into half-cell and carries out electrochemical property test.
Embodiment 4
(1) weighing nickel sulfate, cobaltous sulfate and aluminum sulfate respectively is 21.02kg, 4.2kg, 1.78kg molecular formula LiNi0.8Co0.1Al0.2O2In mole specific concentration stirring be dissolved in deionized water, be configured to the mixing salt solution of 2mol/L；
(2) 17.8kg sodium hydroxide is weighed, for stirring and dissolving in deionized water, the sodium hydroxide for being configured to 4mol/L is molten Liquid is used as precipitating reagent；
(3) 3400ml ammonium hydroxide is measured, is diluted with deionized water, and be configured to the ammonia spirit of 2mol/L, as complexing agent It uses；
(4) constant temperature water bath in reaction kettle is heated to 50 DEG C with the mode of direct electro heating, it is configured by above-mentioned 3 kinds Solution is slowly added dropwise respectively to reaction kettle, and controlling reaction kettle pH value is 9.25, reacts 35h.
(5) continue to be slowly added dropwise to reaction kettle, adjust ammonium hydroxide flow and hydrogen-oxygen above-mentioned 3 kinds of configured solution respectively Changing sodium flow stablizes pH after 10.78, reaction 20h；It is aged after 35h that obtain multilayer hexagonal flake compound with graininess again Nickel cobalt aluminium hydroxide precursor.
(6) above-mentioned coprecipitated product is repeatedly washed, nickel cobalt aluminium ternary material precursor obtained after being dehydrated, drying Particle.
The nickel cobalt aluminium ternary material precursor prepared to the embodiment of the present invention 4 detects, the results showed that, tap density is 2.3g/ml, D50 are 13 μm.
The modifications such as undoped and cladding are obtained after above-mentioned granular precursor is mixed with lithium carbonate, after high-temperature calcination Positive electrode LiNi0.8Co0.1Al0.2O2, it is assembled into half-cell and carries out electrochemical property test.
Embodiment 5
(1) molecular formula LiNi is pressed0.8Co0.1Al0.1O2Nickel sulfate, cobaltous sulfate 21.02kg, 4.2kg are weighed respectively, are configured 2mol/L nickel cobalt salting liquid weighs 3.2kg sodium aluminate solution solution configuration aluminum salt solution；
(2) 35.6kg sodium hydroxide is weighed, for stirring and dissolving in deionized water, the sodium hydroxide for being configured to 8mol/L is molten Liquid is used as precipitating reagent；
(3) 3400ml ammonium hydroxide is measured, is diluted with deionized water, and be configured to the ammonia spirit of 2mol/L, as complexing agent It uses；
(4) constant temperature water bath in reaction kettle is heated to 53 DEG C with the mode of direct electro heating, it is configured by above-mentioned 4 kinds Solution is slowly added dropwise respectively to reaction kettle, and controlling reaction kettle pH value is 11.25, reacts 10h.
(5) continue to be slowly added dropwise to reaction kettle, adjust ammonium hydroxide flow and hydrogen-oxygen above-mentioned 4 kinds of configured solution respectively Changing sodium flow stablizes pH after 11.78, reaction 45h；It is aged after 36h that obtain multilayer hexagonal flake compound with graininess again Nickel cobalt aluminium hydroxide precursor.
(6) above-mentioned coprecipitated product is repeatedly washed, nickel cobalt aluminium ternary material precursor obtained after being dehydrated, drying Particle.
The nickel cobalt aluminium ternary material precursor prepared to the embodiment of the present invention 5 detects, the results showed that, tap density is 2.5g/ml, D50 are 10 μm.
The modifications such as undoped and cladding are obtained after above-mentioned granular precursor is mixed with lithium carbonate, after high-temperature calcination Positive electrode LiNi0.8Co0.1Al0.1O2, it is assembled into half-cell and carries out electrochemical property test.
Embodiment 6
(1) weighing nickel sulfate, cobaltous sulfate and manganese sulfate respectively is 20.34kg, 2.8kg and 13.5kg, according to chemical molecular Formula LiNi0.80Co0.1Mn0.08Al0.02O2In mole specific concentration stirring be dissolved in deionized water, be configured to the salt-mixture of 2mol/L Solution；Sodium aluminate solution is configured to after weighing the dissolution of 1.78Kg sodium aluminate according still further to above-mentioned molecular formula ratio.
(2) 17.8kg sodium hydroxide is weighed, for stirring and dissolving in deionized water, the sodium hydroxide for being configured to 4mol/L is molten Liquid is used as precipitating reagent；
(3) 3400ml ammonium hydroxide is measured, is diluted with deionized water, and be configured to the ammonia spirit of 2mol/L, as complexing agent It uses；
(4) constant temperature water bath in reaction kettle is heated to 50 DEG C with the mode of direct electro heating, it is configured by above-mentioned 4 kinds Solution is slowly added dropwise respectively to reaction kettle, and controlling reaction kettle pH value is 9.25, reacts 18h.
(5) continue to be slowly added dropwise to reaction kettle, adjust ammonium hydroxide flow and hydrogen-oxygen above-mentioned 4 kinds of configured solution respectively Changing sodium flow stablizes pH after 10.78, reaction 40h；It is aged that obtain multilayer hexagonal flake afterwards for 24 hours compound with graininess again Molecular formula be LiNi0.80Co0.1Mn0.08Al0.02O2Nickel cobalt manganese aluminium hydroxide presoma.
(6) above-mentioned coprecipitated product is repeatedly washed, nickel cobalt manganese aluminium quaternary material forerunner obtained after being dehydrated, drying Body particle.
The nickel cobalt manganese aluminium quaternary material presoma prepared to the embodiment of the present invention 6 detects, the results showed that, tap density It is 16 μm for 2.0g/ml, D50.
The modifications such as undoped and cladding are obtained after above-mentioned granular precursor is mixed with lithium carbonate, after high-temperature calcination Positive electrode LiNi0.80Co0.1Mn0.08Al0.02O2, it is assembled into half-cell and carries out electrochemical property test.
Above to a kind of positive electrode material precursor provided by the invention and preparation method thereof, positive electrode and lithium ion battery It is described in detail, used herein a specific example illustrates the principle and implementation of the invention, above The explanation of embodiment is merely used to help understand method and its core concept of the invention, including best mode, and but also Any person skilled in the art can practice the present invention, including any device or system of manufacture and use, and implement any In conjunction with method.It should be pointed out that for those skilled in the art, in the premise for not departing from the principle of the invention Under, it can be with several improvements and modifications are made to the present invention, these improvement and modification also fall into the protection of the claims in the present invention In range.The range of the invention patent protection is defined by the claims, and may include those skilled in the art it is conceivable that Other embodiments.If these other embodiments have the structural element for being not different from claim character express, or If they include the equivalent structural elements with the character express of claim without essence difference, these other embodiments It should be comprising within the scope of the claims.

Claims (10)

1. a kind of positive electrode material precursor, which is characterized in that have the general formula as shown in formula (I):
NixCoyMnzAl1-x-y-z(OH)2(I)；
Wherein, 0 < x < 1,0 < y < 1, x+y < 1,0≤z < 1, x+y+z≤1；
The spheric granules that the positive electrode material precursor forms for six square piece of positive electrode material precursor, and the positive electrode forerunner Positive electrode material precursor nano particle is compounded in six square piece of body.
2. positive electrode material precursor according to claim 1, which is characterized in that six square pieces of the positive electrode material precursor Layered body including six square piece of multilayer composition, or, six square piece of layered body and single layer of six square piece of multilayer composition；
The number of plies of the multilayer is 2~50 layers；
The partial size of the nano particle is 100~300nm；
The mass ratio of six square piece of positive electrode material precursor and the positive electrode material precursor nano particle is 10:(1~5).
3. positive electrode material precursor according to claim 2, which is characterized in that described group becomes stacking and formed；
Six square piece of multilayer with a thickness of 50~200nm；
The piece interlayer of six square piece of multilayer has gap；
The positive electrode material precursor nano-particles reinforcement is on the surface and piece lamellar spacing of six square piece of multilayer.
4. a kind of preparation method of positive electrode material precursor, which comprises the following steps:
1) after mixing nickel salt, manganese salt and/or aluminium salt, cobalt salt and water, mixed liquor is obtained；
2) mixed liquor, complexing agent and alkali is added, after being reacted, obtains the first mixed solution；
3) it into the first mixed solution that above-mentioned steps obtain, after continuously adding mixed liquor, complexing agent and alkali, then secondary response, obtains To the second mixed solution；
4) the second mixed solution for obtaining above-mentioned steps obtains positive electrode material precursor after ageing.
5. the preparation method according to claim 4, which is characterized in that the step 1) specifically:
After nickel salt, manganese salt, cobalt salt and water are mixed, just mixed liquor is obtained；
After aluminium salt and water are mixed, aluminum salt solution is obtained；The molar concentration of the aluminum salt solution is 0.1~2mol/L；
After first mixed liquor and aluminum salt solution are mixed, mixed liquor is obtained.
6. the preparation method according to claim 4, which is characterized in that in the mixed liquor, the manganese salt and/or aluminium salt, The total mol concentration of nickel salt and cobalt salt is 1~3.5mol/L；
The alkali is selected from one of lithium hydroxide, sodium hydroxide and potassium hydroxide or a variety of；
The complexing agent be selected from ammonium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium nitrate and One of urea is a variety of；
In the step 2), the total mole number of the molal quantity of the complexing agent and the nickel salt, manganese salt and/or aluminium salt, cobalt salt Ratio is (1~10): 1；
The pH value of the reaction is 7.5~12.0；
The time of the reaction is 4~36h；
The temperature of the reaction is 40~70 DEG C.
7. the preparation method according to claim 4, which is characterized in that in the step 3), the molal quantity of the complexing agent Ratio with the nickel salt, manganese salt and/or aluminium salt, the total mole number of cobalt salt is (5~20): 1；
The pH value of the secondary response again is 9.5~13.0；
The pH value of the secondary response again is higher than the pH value of reaction by 0.25~2；
The time of the secondary response again is 36~50h；
The temperature of the secondary response again is 45~65 DEG C；
The time of the ageing is 20~40h.
8. a kind of positive electrode, which is characterized in that have the general formula as shown in formula (II):
Li1+wNixCoyMnzAl1-x-y-zO2(II),
Wherein, 0 < x < 1,0 < y < 1, x+y < 1,0≤z < 1, x+y+z≤1, -0.5≤w≤0.5；
The positive electrode is the spheric granules of six square piece of positive electrode composition, and is compounded with just in six square piece of the positive electrode Pole material nanoparticle.
9. positive electrode according to claim 8, which is characterized in that the positive electrode is any one by claims 1 to 3 Before positive electrode prepared by preparation method described in positive electrode material precursor or claim 4~8 any one described in Body is driven, is after heat treatment obtained with lithium salts；
The temperature of the heat treatment is 725 DEG C~1150 DEG C.
10. a kind of lithium ion battery, including positive electrode described in claim 8 or 9.
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