CN104993122A - Ternary precursor material with internally dense and externally loose structure primary particle bulk density, anode material and preparation method thereof - Google Patents

Ternary precursor material with internally dense and externally loose structure primary particle bulk density, anode material and preparation method thereof Download PDF

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CN104993122A
CN104993122A CN201510287483.2A CN201510287483A CN104993122A CN 104993122 A CN104993122 A CN 104993122A CN 201510287483 A CN201510287483 A CN 201510287483A CN 104993122 A CN104993122 A CN 104993122A
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lithium
open structure
ternary precursor
precursor material
bulk density
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CN104993122B (en
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杜春雨
闫春秋
尹鸽平
高云智
左朋建
程新群
马玉林
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Harbin Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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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Abstract

The invention discloses a ternary precursor material with an internally dense and externally loose structure primary particle bulk density, an anode material and a preparation method thereof. The particle of the ternary precursor material has an internally dense and externally loose structure bulk density. The ternary precursor material is NixCoyMn2M1-x-y-z(OH)2 or NixCoyMnzM1-x-y-zCO3, x is greater than 0 and smaller than 1, y is greater than 0 and smaller than 1, z is greater than 0 and smaller than 1, x+y+z is smaller than or equal to 1, M is one or more of Zr, Fe, Sm, Pr, Nb, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La and Bi. According to the invention, based on comprehensive consideration of the tap density and rate performance changing situation, the introduction position and concentration of a surfactant are designed, and the accumulation compactness of particles from the inside to the outside at all parts is regulated, thus finally realizing development of the optimal overall performance of the material. The materials prepared by the method provided by the invention have the characteristics of excellent post-sintering rate and cycle performance, and high tap density.

Description

There is interior solid, the ternary precursor material of primary particle bulk density of outside open structure, positive electrode and preparation method
Technical field
The present invention relates to a kind of lithium ion battery ternary precursor material and preparation method, and the positive electrode be prepared from by this material and preparation method.
Background technology
Lithium ion battery realizes commercialization and the secondary cell becoming most important, be most widely used in the nineties in 20th century.Relative to traditional lead-acid battery and nickel radical battery, lithium ion battery has energy density high (about 100 ~ 150Wh/kg), has extended cycle life, environment compatibility is good, the advantage such as lightweight.As energy source easily, lithium ion battery is widely used in multiple portable type electronic product, and the development for the industry society comprising electronics technology serves great impetus.Also be one of most promising candidate of electric motor car (EV) and hybrid electric vehicle (HEV) energy source simultaneously.In current lithium ion battery technology, positive electrode not only limits cell voltage and capacity, is also Li +the limiting factor of transfer rate.Therefore, the exploitation of positive electrode is particularly crucial for the practical application widely of lithium ion battery, to come into one's own in recent years and extensive concern.
From LiCoO in 1980 2since being proved to be the positive electrode that may become chargeable lithium ion battery, in positive electrode, transition metal embedded oxide receives main concern.High stability due to self structure and the advantage of large-scale production of being more convenient for realizing relative to other materials, cobalt acid lithium (LiCoO 2) in first commercial li-ion battery of Sony company production, be used as positive electrode, but the Li owing to too much deviating from +can aggravate because oxygen layer repels the structural instability caused, therefore for cost and safety problem, people are for LiCoO 2application in electric motor car and other energy storage device is not had an optimistic view of.Lithium nickelate material actual specific capacity is higher, and cost comparatively cobalt acid lithium is lower, but preparation process conditional requires harsh, and because cation mixing causes structural change to make the irreversible capacity of material also comparatively large, in addition, the security performance of material is also unsatisfactory.Layered lithium manganate initial capacity is higher, and cost is also lower, but causes capacity retention undesirable owing to there is John-Teller effect in cyclic process.
As mentioned above, stratiform LiMO 2material (M=Ni, Co, Mn etc.) determines that its practical application is limited due to the defect of self property.Have been reported, basic layered oxide more corresponding during the transition metal ions mixed when there being two kinds at transition metal layer has better electrochemistry and security performance.Based on the synergy between transition metal, nickle cobalt lithium manganate ternary metal oxide material combines LiCoO 2good high rate performance, LiNiO 2high power capacity and due to Mn 4+exist and the structural stability of acquisition.The main electro-chemical activity of material is provided by Ni, and Co only embodies active when high potential.Clearly, Mn does not participate in redox reaction, only plays the effect of rock-steady structure.
As the potential positive electrode of lithium ion battery that can be applicable to the fields such as all kinds of portable electric appts, new energy electric motor vehicle, nickle cobalt lithium manganate ternary metal oxide material require possesses high-energy-density to meet the user demand of equipment under different discharge-rates.As everyone knows, high-energy-density often means height ratio capacity and high compacted density.The change of specific capacity and compacted density is subject to the joint effect of many factors, and namely one of them is the granule interior accumulation tightness of material.On the one hand, granule interior accumulation tightness has a significant effect to the capacity under specific capacity especially high magnification.In certain limit, granule interior accumulation situation is more loose, the wetness degree of electrolyte to material is better, and the resistance of material internal conductivity is less, based on this, in charge and discharge process especially in high power charging-discharging process, the capacity of material plays also to be thought with regard to unreasonable, therefore, especially improves the angle of high rate performance from raising material specific capacity, in the middle of material preparation process, appropriateness should reduce accumulation tightness.On the other hand, granule interior piles up tightness has conclusive effect equally to the compacted density of material.There are some researches show, the principal element affecting nickle cobalt lithium manganate ternary metal oxide material tap density is that granule interior piles up tightness and particle size distribution situation, within the specific limits, granule interior accumulation tightness is larger, material shared volume when filling of equal in quality is less, the tap density of material is also higher, and the compacted density that high-tap density is often corresponding higher, therefore, from the angle optimizing compacted density, in the middle of material preparation process, appropriateness should improve accumulation tightness.
In sum, determine that the specific capacity of material energy densities and compacted density all pile up tightness with granule interior directly related.But with the change of accumulation tightness, specific capacity is but contrary with the variation tendency of compacted density, such as, in certain limit, when piling up tightness raising, the tap density increase of material, but the specific capacity of specific capacity especially under high magnification reduces; Otherwise when piling up tightness and reducing, the specific capacity of specific capacity especially under high magnification increases, but tap density reduces; This just causes when designing the accumulation tightness structure of particle, must consider its Different Effects rule to specific capacity and tap density, to realize the optimum of energy density.In other words, under the prerequisite of not obvious weakening material high power capacity attribute, the energy density lifting contribution of tap density to material improving material is maximum.
Summary of the invention
The present invention is based on granule interior and pile up the adverse effect of tightness to material tap density and high rate performance, provide and a kind of there is interior solid, the ternary precursor material of primary particle bulk density of outside open structure and preparation method and the positive electrode be prepared from by this ternary precursor material and preparation method, achieve based on considering tap density and high rate performance situation of change, by introducing position and the concentration of design surface activating agent, the accumulation tightness of regulation and control particle various piece from inside to outside, the combination property finally realizing material optimum plays.
The object of the invention is to be achieved through the following technical solutions:
A kind of lithium ion battery ternary precursor material of primary particle bulk density with interior solid, outside open structure, the particle of described ternary precursor material has piles up tightness interior solid, outside open structure, namely building up inside tightness is greater than outside accumulation tightness, and ternary precursor material is Ni xco ymn zm 1-x-y-z(OH) 2or Ni xco ymn zm 1-x-y-zcO 30<x<1,0<y<1,0<z<1, x+y+z≤1, M is one or more in Zr, Fe, Sm, Pr, Nb, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La, Bi.
In above-mentioned ternary precursor material, its component structure is characterised in that particle optional position chemical element component numerical value identical (being preferably x:y:z=8:1:1, x:y:z=5:2:3, x:y:z=1:1:1, x:y:z=4:2:4 etc.).According to the principle considering material electrochemical performance and tap density, when chemical constituent value can make material body play good electrical chemical property especially high rate performance time (as x:y:z=8:1:1), increase the inner surfactant concentration introduced, to promote tap density; When chemical constituent value can not make material body play good electrical chemical property especially high rate performance time (as x:y:z=1:1:1), reduce the inner surfactant concentration introduced, to ensure that the not obvious material electrochemical performance that affects of the introducing of surfactant plays.
In above-mentioned ternary precursor material, interior solid layer and outside weaker zone Thickness Ratio scope are 1:50-50:1.
In above-mentioned ternary precursor material, described second particle average grain diameter is 1-40 μm, and tap density is 1-4g/cm 3.
The above-mentioned preparation method of lithium ion battery ternary precursor material of primary particle bulk density with interior solid, outside open structure, comprises the steps:
One, be nickel by mol ratio: the mixed metal salt of cobalt: manganese: M=x:y:z:1-x-y-z is made into the aqueous solution a1 that concentration is A (0.01mol/L<A<20 mol/L);
Two, surfactant being configured to concentration is B(0.01mol/L<B<20 mol/L) aqueous solution b1;
Three, configuration concentration is the precipitation reagent aqueous solution c1 (0.01mol/L<C<20 mol/L) of C respectively, and concentration is the complexing agent aqueous solution d1 (0.01mol/L<D<20 mol/L) of D;
Four, enveloping agent solution d1, aqueous surfactant solution b1 and deionized water are added in reactor according to the mol ratio (0.01≤x≤100) of 1:6:x, as liquid V1 at the bottom of the reaction in zero moment;
Five, by mixed metal salt a1 solution, precipitation reagent water c1 solution, complexing agent water d1 solution with 1:2:1(precipitation reagent for hydroxide time) or 1:1:1(precipitation reagent is carbonate time) feed rate than inject continuous stirring Liquid-phase reactor, reaction condition is as follows: inert atmosphere, pH value is 6-14, constant temperature 35-85 DEG C, the reaction time is t1 (0<t1<100h);
Six: surfactant solution b1 is added reactor in zero moment, arranged in pairs or groups by the feed rate of control a1, b1, c1, d1, the concentration moment of surfactant is made to maintain the value same with liquid phase of the initial end, total interpolation time of surfactant is t2(t2<t1,0<t2<100h);
Seven: when reaction proceeds to the t2 moment, suspend charging, by solution left standstill sedimentation in reactor, sedimentation time is t3(0<t3<10h), after sedimentation completes, all supernatants being dissolved with surfactant in removing reactor, and add liquid V1 at the bottom of isopyknic reaction substitute, continue the process conditions charging according to step 5, react to the t1 moment, obtained have the Ni that accumulation tightness is interior solid, outside open structure xco ymn zm 1-x-y-z(OH) 2or Ni xco ymn zm 1-x-y-zcO 3material.
In the preparation method of above-mentioned lithium ion battery ternary precursor material, described surfactant is a kind of or wherein several mixture of sulfuric acid (sulfuric acid of fatty alcohol sulphuric acid, secondary alkyl sulfate, polyoxyethylene alkyl ether sulfate salt, derivative of fatty acid) or sulfonate (alkylbenzenesulfonate, alkylnaphthalene sulfonate, alkyl sulfonate, petroleum sulfonate, lignosulfonates etc.).
In the preparation method of above-mentioned lithium ion battery ternary precursor material, in described nickel cobalt manganese salt-mixture, nickel salt is a kind of or wherein several mixture in nickelous sulfate, nickel nitrate, nickel acetate, nickel chloride, cobalt salt is a kind of or wherein several mixture in cobaltous sulfate, cobalt nitrate, cobalt acetate, cobalt chloride, and manganese salt is a kind of or wherein several mixture in manganese sulfate, manganese nitrate, manganese acetate, manganese chloride.
In the preparation method of above-mentioned lithium ion battery ternary precursor material, described M salt is a kind of or wherein several mixture of soluble sulphate, nitrate, acetate, chlorate, citrate, alkoxide.
In the preparation method of above-mentioned lithium ion battery ternary precursor material, described complexing agent is a kind of or wherein several mixture in ammoniacal liquor, ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, EDTA, ammonium citrate, ethylenediamine, acetic acid, sodium fluoride, tartaric acid, maleic acid, butanedioic acid, citric acid, malonic acid, and the mol ratio of complexing agent and the total salt of metal is 0.1-10.0.
In the preparation method of above-mentioned lithium ion battery ternary precursor material, for Ni xco ymn zm 1-x-y-z(OH) 2material, described precipitation reagent is a kind of or wherein several mixture in NaOH, potassium hydroxide, lithium hydroxide; For Ni xco ymn zm 1-x-y-zcO 3material, described precipitation reagent is a kind of or wherein several mixture in sodium carbonate, potash, lithium carbonate; The mol ratio of precipitation reagent and the total salt of metal is 0.1-4.0.
There is the anode material for lithium ion battery of primary particle bulk density for interior solid, outside open structure, for what be prepared from by above-mentioned ternary precursor material and lithium source, there is the LiNi piling up tightness interior solid, outside open structure xco ymn zm 1-x-y-zo 2material.
A kind of preparation method of above-mentioned anode material for lithium ion battery, comprise the steps: by have interior solid, outside open structure the lithium ion battery ternary precursor material of primary particle bulk density with lithium source according to mol ratio 1:(1 ~ 1.25) mix, under pure oxygen or air atmosphere, 1-45h is sintered at 500-1000 DEG C, after vibration screening, obtain the LiNi piling up tightness interior solid, outside open structure xco ymn zm 1-x-y-zo 2material.
In the preparation method of above-mentioned anode material for lithium ion battery, described lithium source is a kind of or wherein several mixture in lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride, lithium fluoride, lithium oxalate, lithium phosphate, lithium hydrogen phosphate, lithium carbonate.
Above-mentioned anode material for lithium ion battery can form lithium ion battery with negative pole, barrier film, electrolyte etc.
The present invention has following advantage:
1, architectural feature of the present invention is that realizing particle has accumulation tightness interior solid, outside loose structure (Fig. 1).It is characterized in that the surfactant concentration by introducing in differential responses phase change, this material granule is made to have the different structure of inside and outside accumulation density, namely inside is outside more fine and close, outside is more inner more loose, according to the principle considering material electrochemical performance and tap density, when chemical constituent value can make material body play good electrical chemical property especially high rate performance time (as x:y:z=8:1:1), increase the inner surfactant concentration introduced, to promote tap density; When chemical constituent value can not make material body play good electrical chemical property especially high rate performance time (as x:y:z=1:1:1), reduce the inner surfactant concentration introduced, to ensure that the not obvious material electrochemical performance that affects of the introducing of surfactant plays.Component characteristics is that chemical constituent numerical value in optional position is consistent from inside to outside at particle.
2, the material prepared of the method is adopted to have multiplying power after sintering and cycle performance is excellent, tap density is high feature.
3, preparation technology of the present invention is simple, and lower cost for material, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is particle packing density interior solid, outside loose schematic diagram;
Fig. 2 is that comparative example does not add surfactant and reacts the SEM pattern after 12 hours;
Fig. 3 is that embodiment adds surfactant and reacts the SEM pattern after 12 hours;
Fig. 4 is that comparative example does not add surfactant and reacts the SEM pattern after 24 hours;
Fig. 5 is that embodiment adds surfactant and reacts the SEM pattern after 24 hours;
Fig. 6 is that comparative example does not add surfactant and reacts the adsorption isothermal curve test result after 24 hours;
Fig. 7 is that embodiment adds surfactant and reacts the adsorption isothermal curve test result after 24 hours;
Fig. 8 is the high rate performance test result of comparative example and embodiment;
Fig. 9 be comparative example do not add surfactant react 24 hours after sintering after the first charge-discharge curve of material;
Figure 10 be embodiment add surfactant react 24 hours after sintering after the first charge-discharge curve of material.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
The evaluation of material mode of comparative example and embodiment is: material after obtained persursor material and sintering is carried out particle size distribution, tap density and BET specific surface area respectively and characterizes, and carries out electrochemistry multiplying power and first charge-discharge volumetric properties sign to material after sintering.
comparative example 1
Preparation mol ratio is Ni:Co:Mn=8:1:1 and total concentration is nickelous sulfate, manganese sulfate, the cobaltous sulfate mixed salt solution of 2mol/L, the complexing agent ammonia spirit of 2.8mol/L, the precipitation reagent sodium hydroxide solution of 2mol/L.By metal salt solution, ammonia spirit, sodium hydroxide solution with given pace than adding in the reactor of high-speed stirred, control the pH of whole reaction system 10 ± 0.3, temperature controls at 58 DEG C, react after 24 hours, after cleaning, cross the soluble impurity filtered in material, under vacuum atmosphere, dry material, by drying material and lithium hydroxide with the mixed in molar ratio of 1:1.05, under pure oxygen atmosphere, 900 DEG C sinter 24 hours, obtain LiNi 0.73co 0.12mn 0.15o 2powder.
After tested, react to 12 hours persursor material specific areas be 2.3m 2/ g, react to 24 hours persursor material specific areas be 0.95m 2/ g, the median D50 of persursor material is 11.2 μm, and tap density is 1.88g/cm 3, the rear material of sintering first discharge capacity is 196mAh/g, and circulate 30 capacity retention 84%, 0.5C capacity 183mAh/g, 1C capacity 176mAh/g.
Five, by mixed metal salt a1 solution, precipitation reagent water c1 solution, complexing agent water d1 solution with 1:2:1(precipitation reagent for hydroxide time) or 1:1:1(precipitation reagent is carbonate time) feed rate than inject continuous stirring Liquid-phase reactor, reaction condition is as follows: inert atmosphere, pH value is 6-14, constant temperature 35-85 DEG C, the reaction time is t1 (0<t1<100h);
Six: surfactant solution b1 is added reactor in zero moment, arranged in pairs or groups by the feed rate of control a1, b1, c1, d1, the concentration moment of surfactant is made to maintain the value same with liquid phase of the initial end, total interpolation time of surfactant is t2(t2<t1,0<t2<100h);
Seven: when reaction proceeds to the t2 moment, suspend charging, by solution left standstill sedimentation in reactor, sedimentation time is t3(0<t3<10h), after sedimentation completes, all supernatants being dissolved with surfactant in removing reactor, and add liquid V1 at the bottom of isopyknic reaction substitute, continue the process conditions charging according to step 5, react to the t1 moment, obtained have the Ni that accumulation tightness is interior solid, outside open structure xco ymn zm 1-x-y-z(OH) 2or Ni xco ymn zm 1-x-y-zcO 3material.
embodiment 1
Preparation mol ratio is Ni:Co:Mn=8:1:1 and total concentration is nickelous sulfate, manganese sulfate, the cobaltous sulfate metal salt solution of 2mol/L, the complexing agent ammonia spirit of 2.8mol/L, the precipitation reagent sodium hydroxide solution of 2mol/L, the dodecyl sodium sulfate hydrothermal solution of 1mol/L.Enveloping agent solution, deionized water, aqueous surfactant solution are total to 800ml solution according to the mol ratio of 1:6:1 and add in reactor, as liquid at the bottom of the reaction in zero moment, by metal salt solution, the complexing agent ammonia spirit of 2.8mol/L and the precipitation reagent sodium hydroxide solution of 2mol/L add in the reactor of high-speed stirred with given pace ratio (1:1:2), wherein dodecyl sodium sulfate mixed solution was introduced at first 12 hours, control the pH of whole reaction system 10 ± 0.3, temperature controls at 58 DEG C, react after 12 hours, suspend charging, by solution left standstill sedimentation in reactor, sedimentation time is 1h, after sedimentation completes, all supernatants being dissolved with surfactant in removing reactor, and add liquid at the bottom of isopyknic reaction substitute, continue the pH of the whole reaction system of control 10 ± 0.3, temperature controls at 58 DEG C, react after 24 hours, by material through cleaning, after crossing the soluble impurity filtered in material, obtain Ni 0.8co 0.1mn 0.1(OH) 2, under vacuum atmosphere, dry material, by drying material and lithium hydroxide with the mixed in molar ratio of 1:1.05, under pure oxygen atmosphere, 900 DEG C of sintering 24 hours, obtain LiNi 0.8co 0.1mn 0.1o 2powder, this material granule piles up tightness interior solid, outside loose, and chemical constituent is all consistent at an arbitrary position.
After tested, adding surfactant reaction is 0.52m to specific area after 12 hours 2/ g, reacting specific area after 24 hours is 0.36m 2/ g, the median D50 of this persursor material is 10 μm, and tap density is 2.2g/cm 3, after sintering, discharge capacity is 198mAh/g first, and circulate 30 capacity retention 81%, 0.5C capacity 185 mAh/g, 1C capacity 175mAh/g.
By Fig. 2, Fig. 3 contrast after can see, after adding surfactant, the accumulation tightness of material is higher, particle grow more closely knit.
Can see after being contrasted by Fig. 4, Fig. 5, because latter 12 hours do not introduce surfactant, the accumulation density therefore not observing material surface from surface sweeping Electronic Speculum figure has significant change.
Shown by the BET test result of Fig. 6, Fig. 7, introduce after surfactant, the specific area of material is less, coincide with sem test result, and further demonstrating surfactant, that Material growth can be impelled to obtain is more closely knit.
The experimental result of Fig. 8 shows, the introducing of surfactant can weaken the high rate performance of material to a certain extent, but the weakening degree of high rate performance not obvious.
First charge-discharge capacity comparison result display in Fig. 9, Figure 10, after introducing surfactant, the capacity first of material is not subject to obvious impact, and difference of them is not obvious.
embodiment 2
Preparation mol ratio is Ni:Co:Mn=8:1:1 and total concentration is nickelous sulfate, manganese sulfate, the cobaltous sulfate metal salt solution of 2mol/L, the complexing agent ammonia spirit of 2.8mol/L, the precipitation reagent sodium carbonate liquor of 2mol/L, the dodecyl sodium sulfate hydrothermal solution of 1mol/L.Enveloping agent solution, deionized water, aqueous surfactant solution are total to 800ml solution according to the mol ratio of 1:6:1 and add in reactor, as liquid at the bottom of the reaction in zero moment, by metal salt solution, the complexing agent ammonia spirit of 2.8mol/L and the precipitation reagent sodium carbonate liquor of 2mol/L add in the reactor of high-speed stirred with given pace ratio (1:1:1), wherein dodecyl sodium sulfate mixed solution was introduced at first 12 hours, control the pH of whole reaction system 10 ± 0.3, temperature controls at 58 DEG C, react after 12 hours, suspend charging, by solution left standstill sedimentation in reactor, sedimentation time is 1h, after sedimentation completes, all supernatants being dissolved with surfactant in removing reactor, and add liquid at the bottom of isopyknic reaction substitute, continue the pH of the whole reaction system of control 10 ± 0.3, temperature controls at 58 DEG C, react after 24 hours, by material through cleaning, after crossing the soluble impurity filtered in material, obtain Ni 0.8co 0.1mn 0.1cO 3, under vacuum atmosphere, dry material, by drying material and lithium hydroxide with the mixed in molar ratio of 1:1.05, under pure oxygen atmosphere, 900 DEG C of sintering 24 hours, obtain LiNi 0.8co 0.1mn 0.1o 2powder, this material granule piles up tightness interior solid, outside loose, and chemical constituent is all consistent at an arbitrary position.
embodiment 3
The difference of the present embodiment and embodiment 1 is: precipitation reagent is the mixture of NaOH and potassium hydroxide, and the mol ratio of the two is 1:1; Lithium source is the mixture of lithium hydroxide and lithium nitrate and lithium sulfate, and the mol ratio of lithium hydroxide, lithium nitrate, lithium sulfate is 1:1:2.
embodiment 4
The difference of the present embodiment and embodiment 1 is: complexing agent is the mixture of ammoniacal liquor and ammonium chloride, the mixture of the mol ratio of the two to be 1:1, M be chromium and aluminium, and exists with the form of chromium sulfate and aluminum sulfate respectively, and the mol ratio of the two is 1:1.
embodiment 5
The difference of the present embodiment and embodiment 1 is: surfactant is the mixture of lauryl sodium sulfate and sodium cetanesulfonate and neopelex, and the mol ratio of lauryl sodium sulfate, sodium cetanesulfonate, neopelex is 10:1:2.
embodiment 6
The difference of the present embodiment and embodiment 1 is: corresponding to slaine, anion is chosen for nitrate anion, i.e. nickel nitrate, cobalt nitrate, manganese nitrate.
embodiment 7
The difference of the present embodiment and embodiment 1 is: the mol ratio of Ni:Co:Mn is 4:3:3.
embodiment 8
The difference of the present embodiment and embodiment 1 is: the mol ratio of Ni:Co:Mn is 5:2:3.
embodiment 9
The difference of the present embodiment and embodiment 2 is: precipitation reagent is the mixture of sodium carbonate and potash, and the mol ratio of sodium carbonate, potash is 3:1; Lithium source is the mixture of lithium hydroxide and lithium nitrate and lithium oxalate, and the mol ratio of lithium hydroxide, lithium nitrate, lithium oxalate is 5:2:1.
embodiment 10
The difference of the present embodiment and embodiment 2 is: complexing agent is the mixture of ammoniacal liquor and ammonium nitrate, the mixture of the mol ratio of ammoniacal liquor, ammonium nitrate to be 5:1, M be chromium and magnesium, and exists with the form of chromic nitrate and magnesium sulfate respectively, and the mol ratio of the two is 1:1.
embodiment 11
The difference of the present embodiment and embodiment 2 is: surfactant is chosen for the mixture of lauryl sodium sulfate and dodecyl sodium sulfate, and the mol ratio of lauryl sodium sulfate and dodecyl sodium sulfate is 2:1.
embodiment 12
The difference of the present embodiment and embodiment 2 is: corresponding to slaine, anion is chosen for chloride ion, i.e. nickel chloride, cobalt chloride, manganese chloride.
embodiment 13
The difference of the present embodiment and embodiment 2 is: the mol ratio of Ni:Co:Mn is 4:3:3.
embodiment 14
The difference of the present embodiment and embodiment 2 is: the mol ratio of Ni:Co:Mn is 5:2:3.

Claims (10)

1. one kind has the ternary precursor material of primary particle bulk density of interior solid, outside open structure, it is characterized in that the particle of described ternary precursor material has and pile up tightness interior solid, outside open structure, namely building up inside tightness is greater than outside accumulation tightness, and ternary precursor material is Ni xco ymn zm 1-x-y-z(OH) 2or Ni xco ymn zm 1-x-y-zcO 30<x<1,0<y<1,0<z<1, x+y+z≤1, M is one or more in Zr, Fe, Sm, Pr, Nb, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La, Bi.
2. the ternary precursor material of primary particle bulk density with interior solid, outside open structure according to claim 1, is characterized in that in described accumulation tightness interior solid, outside open structure, the inside and outside chemical constituent of material is identical.
3. the ternary precursor material of primary particle bulk density with interior solid, outside open structure according to claim 1, it is characterized in that the second particle average grain diameter of described ternary precursor material is 1-40 μm, tap density is 1-4g/cm 3.
4. the preparation method of ternary precursor material of primary particle bulk density with interior solid, outside open structure according to claim 1, is characterized in that described method step is as follows:
One, be nickel by mol ratio: the mixed metal salt of cobalt: manganese: M=x:y:z:1-x-y-z is made into the aqueous solution a1 that concentration is A, 0.01mol/L<A<20 mol/L;
Two, surfactant is configured to the aqueous solution b1 that concentration is B, 0.01mol/L<B<20 mol/L;
Three, the complexing agent aqueous solution d1 of configuration concentration to be the precipitation reagent aqueous solution c1 of C and concentration be D respectively, 0.01mol/L<C<20 mol/L, 0.01mol/L<D<20 mol/L;
Four, enveloping agent solution d1, deionized water, aqueous surfactant solution b1 are added continuously in stirring Liquid-phase reactor according to the molar ratio of 1:6:x, 0.01≤x≤100, as liquid V1 at the bottom of the reaction in zero moment;
Five, mixed salt solution a1, precipitation reagent aqueous solution c1, complexing agent aqueous solution d1 are injected continuous stirring Liquid-phase reactor with the feed rate of 1:2:1 or 1:1:1 ratio, reaction condition is as follows: inert atmosphere, pH value is 6-14, constant temperature 35-85 DEG C, reaction time is t1,0<t1<100h;
Six: surfactant solution b1 is added reactor in zero moment, arranged in pairs or groups by the feed rate of control a1, b1, c1, d1, the concentration moment of surfactant is made to maintain the value same with liquid phase of the initial end, total interpolation time of surfactant is t2, t2<t1,0<t2<100h;
Seven: when reaction proceeds to the t2 moment, suspend charging, by solution left standstill sedimentation in reactor, the sedimentation time is t3,0<t3<10h, after sedimentation completes, be dissolved with the supernatant of surfactant in removing reactor, and add liquid V1 at the bottom of isopyknic reaction and substitute, continue the process conditions charging according to step 5, reaction is to the t1 moment, and obtained have the Ni that accumulation tightness is interior solid, outside open structure xco ymn zm 1-x-y-z(OH) 2or Ni xco ymn zm 1-x-y-zcO 3material.
5. the preparation method of ternary precursor material of primary particle bulk density with interior solid, outside open structure according to claim 4, is characterized in that described Ni xco ymn zm 1-x-y-z(OH) 2or Ni xco ymn zm 1-x-y-zcO 3the chemical constituent of material is consistent in particle optional position.
6. according to claim 4 have interior solid, the preparation method of the ternary precursor material of the primary particle bulk density of outside open structure, it is characterized in that described surfactant is sulfuric acid and/or sulfonate, wherein: sulfuric acid is fatty alcohol sulphuric acid, secondary alkyl sulfate, polyoxyethylene alkyl ether sulfate salt, a kind of or wherein several mixture in the sulfuric acid of derivative of fatty acid, sulfonate is alkylbenzenesulfonate, alkylnaphthalene sulfonate, alkyl sulfonate, petroleum sulfonate, a kind of or wherein several mixture in lignosulfonates, described nickel salt is a kind of or wherein several mixture in nickelous sulfate, nickel nitrate, nickel acetate, nickel chloride, cobalt salt is a kind of or wherein several mixture in cobaltous sulfate, cobalt nitrate, cobalt acetate, cobalt chloride, manganese salt is a kind of or wherein several mixture in manganese sulfate, manganese nitrate, manganese acetate, manganese chloride, and M salt is a kind of or wherein several mixture of soluble sulphate, nitrate, acetate, chlorate, citrate, alkoxide, described complexing agent is a kind of or wherein several mixture in ammoniacal liquor, ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, EDTA, ammonium citrate, ethylenediamine, acetic acid, sodium fluoride, tartaric acid, maleic acid, butanedioic acid, citric acid, malonic acid, for Ni xco ymn zm 1-x-y-z(OH) 2material, described precipitation reagent is a kind of or wherein several mixture in NaOH, potassium hydroxide, lithium hydroxide, and the feed rate of mixed salt solution a1, precipitation reagent aqueous solution c1, complexing agent aqueous solution d1 is than being 1:2:1, for Ni xco ymn zm 1-x-y-zcO 3material, described precipitation reagent is a kind of or wherein several mixture in sodium carbonate, potash, lithium carbonate, and the feed rate of mixed salt solution a1, precipitation reagent aqueous solution c1, complexing agent aqueous solution d1 is than being 1:1:1.
7. the preparation method of ternary precursor material of primary particle bulk density with interior solid, outside open structure according to claim 4, it is characterized in that the mol ratio of complexing agent described in step 5 and the total salt of metal is 0.1-10.0, the mol ratio of precipitation reagent and the total salt of metal is 0.1-4.0.
8. there is the anode material for lithium ion battery of primary particle bulk density for interior solid, outside open structure, it is characterized in that described positive electrode piles up the LiNi that tightness is interior solid, outside open structure for having of being prepared from by ternary precursor material described in claim 1 and lithium source xco ymn zm 1-x-y-zo 2material.
9. the preparation method of anode material for lithium ion battery of primary particle bulk density with interior solid, outside open structure according to claim 8, it is characterized in that described method step is as follows: by have interior solid, outside open structure the lithium ion battery ternary precursor material of primary particle bulk density with lithium source according to mol ratio 1:(1 ~ 1.25) mix, under pure oxygen or air atmosphere, 1-45h is sintered at 500-1000 DEG C, after vibration screening, obtain the LiNi of interior solid, outside open structure xco ymn zm 1-x-y-zo 2material.
10. the preparation method of anode material for lithium ion battery of primary particle bulk density with interior solid, outside open structure according to claim 9, is characterized in that described lithium source is a kind of or wherein several mixture in lithium hydroxide, lithium nitrate, lithium sulfate, lithium chloride, lithium fluoride, lithium oxalate, lithium phosphate, lithium hydrogen phosphate, lithium carbonate.
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