CN104993122B - There is ternary precursor material, positive electrode and the preparation method of the primary particle bulk density of interior solid, outside open structure - Google Patents
There is ternary precursor material, positive electrode and the preparation method of the primary particle bulk density of interior solid, outside open structure Download PDFInfo
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- CN104993122B CN104993122B CN201510287483.2A CN201510287483A CN104993122B CN 104993122 B CN104993122 B CN 104993122B CN 201510287483 A CN201510287483 A CN 201510287483A CN 104993122 B CN104993122 B CN 104993122B
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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
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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
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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
- H01M4/52—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
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses ternary precursor material, positive electrode and the preparation method of a kind of primary particle bulk density with interior solid, outside open structure.The granule of described ternary precursor material has accumulation compactness interior solid, outside open structure, and ternary precursor material is NixCoyMn2M1‑x‑y‑z(OH)2Or NixCoyMnzM1‑x‑y‑zCO3, 0 < 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.Present invention achieves 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 compactness of regulation and control granule various piece from inside to outside, finally realize the optimum combination property of material and play.Material prepared by the present invention has multiplying power after sintering and cycle performance is excellent, tap density is high feature.
Description
Technical field
The present invention relates to a kind of lithium ion battery ternary precursor material and preparation method, and prepared by this material and
The positive electrode become and preparation method.
Background technology
Lithium ion battery realizes commercialization the secondary electricity becoming most important, being most widely used in the nineties in 20th century
Pond.Relative to traditional lead-acid battery and nickel radical battery, lithium ion battery has high (the 100～150Wh/kg left sides of energy density
Right), have extended cycle life, environment compatibility is good, the advantage such as lightweight.As convenient energy source, lithium ion battery is by extensively
General being applied in multiple portable type electronic product, the development for the industry society including electronics technology serves greatly
Impetus.Also it is simultaneously one of the most promising candidate of electric motor car (EV) and hybrid electric vehicle (HEV) energy source.At mesh
In front lithium ion battery technology, positive electrode not only limits cell voltage and capacity, is also Li+The restriction of transfer rate because of
Element.Therefore, the exploitation of positive electrode is particularly critical for the widely actual application of lithium ion battery, in recent years by weight
Depending on and extensive concern.
From LiCoO in 19802Since being proved to be likely to become the positive electrode of chargeable lithium ion battery, at positive electrode
In, transition metal embedded oxide receives and is primarily upon.Due to the high stability of self structure with relative to other materials
Be more convenient for realizing the advantage of large-scale production, cobalt acid lithium (LiCoO2) electric in first commercial li-ion of Sony company production
Pond is used as positive electrode, but due to the Li of too much abjection+Can aggravate owing to oxygen layer repels the structural instability caused
Property, therefore for cost and safety problem, people are for LiCoO2Application in electric motor car and other energy storage device is not seen
Good.Lithium nickelate material actual specific capacity is higher, and cost relatively cobalt acid lithium is lower, but preparation process conditional requires harshness, due to
Cation mixing causes structural change to make the irreversible capacity of material the most greatly, it addition, the security performance of material also and is paid no attention to
Think.Layered lithium manganate initial capacity is higher, and cost is relatively low, but owing to occurring John-Teller effect to cause in cyclic process
Capacity retention is undesirable.
As it has been described above, stratiform LiMO2Material (M=Ni, Co, Mn etc.) determines its actual application due to the defect of self property
Limited.It has been reported that when the basic stratiform oxidation more corresponding when transition metal layer has two kinds of transition metal ionss mixed
Thing has more preferable electrochemistry and security performance.Based on the synergism between transition metal, nickle cobalt lithium manganate ternary metal aoxidizes
Thing material combines LiCoO2Good high rate performance, LiNiO2High power capacity and due to Mn4+The structure existed and obtain is steady
Qualitative.The main electro-chemical activity of material is provided by Ni, and Co only embodies activity when high potential.It is obvious that Mn does not join
With redox reaction, only serve the effect of rock-steady structure.
As lithium ion battery potential that can be applicable to the fields such as all kinds of portable electric appts, new energy electric motor vehicle
Positive electrode, nickle cobalt lithium manganate ternary metal oxide material need possess under different discharge-rates high-energy-density with
Meet the use demand of equipment.It is known that high-energy-density often means that height ratio capacity and high compacted density.Specific capacity with
The change of compacted density is by the joint effect of many factors, and one of them is i.e. the granule building up inside compactness of material.One
Aspect, the capacity under specific capacity especially high magnification is had a significant effect by granule building up inside compactness.In certain limit, granule
Building up inside situation is the most loose, and electrolyte is the best to the wetness degree of material, and the resistance of material internal conductivity is the least, base
In this, in charge and discharge process especially during high power charging-discharging, the capacity of material plays the most preferable, therefore, from
Raising material specific capacity especially improves the angle of high rate performance and sets out, in the middle of material preparation process, it should appropriateness reduces heap
Long-pending compactness.On the other hand, granule building up inside compactness has conclusive effect equally to the compacted density of material.Grind
Studying carefully and show, the principal element affecting nickle cobalt lithium manganate ternary metal oxide material tap density is that granule building up inside is tight
Density and particle size distribution situation, within the specific limits, granule building up inside compactness is the biggest, and the material of equal in quality is being filled out
When filling, shared volume is the least, and the tap density of material is the highest, and the most corresponding higher compacted density of high-tap density,
Therefore, from the angle optimizing compacted density, in the middle of material preparation process, it should appropriateness improves piles up compactness.
In sum, determine that the specific capacity of material energy densities is all direct with granule building up inside compactness with compacted density
Relevant.But with piling up compactness change, specific capacity is the most contrary with the variation tendency of compacted density, such as, in certain limit, work as heap
When long-pending compactness improves, the tap density of material increases, but the specific capacity under specific capacity especially high magnification reduces；Otherwise,
When piling up compactness and reducing, the specific capacity under specific capacity especially high magnification increases, but tap density reduces；This results in
When designing the accumulation compactness structure of granule, it is necessary to consider its Different Effects rule to specific capacity and tap density,
To realize the optimum of energy density.In other words, on the premise of inconspicuous weakening material high power capacity attribute, improve the jolt ramming of material
Density promotes contribution maximum to the energy density of material.
Summary of the invention
The present invention based on granule building up inside compactness to material tap density and the adverse effect of high rate performance, it is provided that
The ternary precursor material of a kind of primary particle bulk density with interior solid, outside open structure and preparation method and by
Positive electrode that this ternary precursor material is prepared from and preparation method, it is achieved that based on considering tap density and multiplying power
Performance situation of change, by introducing position and the concentration of design surface activating agent, the heap of regulation and control granule various piece from inside to outside
Long-pending compactness, finally realizes the optimum combination property of material and plays.
It is an object of the invention to be achieved through the following technical solutions:
A kind of lithium ion battery ternary forerunner of the primary particle bulk density with interior solid, outside open structure
Body material, the granule of described ternary precursor material has accumulation compactness interior solid, outside open structure, i.e. building up inside
Compactness piles up compactness more than outside, and ternary precursor material is NixCoyMnzM1-x-y-z(OH)2Or NixCoyMnzM1-x-y- zCO3, 0 ＜ x ＜ 1,0 ＜ y ＜ 1,0 ＜ z ＜ 1, x+y+z≤1, M is Zr, Fe, Sm, Pr, Nb, Ga, Zn, Y, Mg, Al, Cr, Ca,
One or more in Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La, Bi.
In above-mentioned ternary precursor material, its component structure is characterised by granule optional position chemical element component numerical value phase
With (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 considering
Material electrochemical performance and the principle of tap density, when chemical constituent value can make material body play good electrical chemical property
Especially (such as x: y: z=8: 1: 1) during high rate performance, increase the internal surfactant concentration introduced, to promote tap density；
When chemical constituent value can not make material body performance good electrical chemical property especially high rate performance (such as x: y: z=1: 1:
1), the internal surfactant concentration introduced is reduced, to ensure that the introducing of surfactant not appreciably affects material electrochemical
Can play.
In above-mentioned ternary precursor material, interior solid layer and outside weaker zone thickness are 1: 50-50: 1 than scope.
In above-mentioned ternary precursor material, described second particle mean diameter is 1-40 μm, and tap density is 1-4g/cm3。
A kind of lithium ion battery ternary of the above-mentioned primary particle bulk density with interior solid, outside open structure
The preparation method of persursor material, comprises the steps:
One, it is nickel by mol ratio: cobalt: manganese: it is A that the mixed metal salt of M=x: y: z: 1-x-y-z is made into concentration
The aqueous solution a1 of (0.01mol/L ＜ A ＜ 20mol/L)；
Two, surfactant is configured to the aqueous solution b1 that concentration is B (0.01mol/L ＜ B ＜ 20mol/L)；
Three, being respectively configured the precipitant aqueous solution c1 (0.01mol/L ＜ C ＜ 20mol/L) that concentration is C, concentration is the network of D
Mixture aqueous solution d1 (0.01mol/L ＜ D ＜ 20mol/L)；
Four, by enveloping agent solution d1, aqueous surfactant solution b1 and deionized water according to 1: 6: x mol ratio (0.01
≤ x≤100) add in reactor, as liquid V1 at the bottom of the reaction in zero moment；
Five, by mixed metal salt a1 solution, precipitant water c1 solution, chelating agent water d1 solution, (precipitant is as hydrogen with 1: 2: 1
During oxide) or the feed rate ratio injection continuous stirring Liquid-phase reactor of 1: 1: 1 (when precipitant is carbonate), reaction condition
As follows: inert atmosphere, pH value is 6-14, constant temperature 35-85 DEG C, and the response time is t1 (0 ＜ t1 ＜ 100h)；
Six: surfactant solution b1 is added reactor in zero moment, by controlling the feed rate of a1, b1, c1, d1
Collocation so that the concentration moment of surfactant maintains the value same with liquid phase of the initial end, always adding the time of surfactant
For t2 (t2 ＜ t1,0 ＜ t2 ＜ 100h)；
Seven: when reaction was carried out to the t2 moment, suspending charging, settled by solution left standstill in reactor, the sedimentation time is t3 (0
＜ t3 ＜ 10h), after having settled, remove all supernatant dissolved with surfactant in reactor, and add isopyknic instead
Should substitute by end liquid V1, continue to feed according to the process conditions of step 5, react to after the t1 moment, prepare and there is accumulation compactness be
Interior solid, the Ni of outside open structurexCoyMnzM1-x-y-z(OH)2Or NixCoyMnzM1-x-y-zCO3Material.
In the preparation method of above-mentioned lithium ion battery ternary precursor material, described surfactant is sulfuric acid
(fatty alcohol sulphuric acid, secondary alkyl sulfate, polyoxyethylene alkyl ether sulfate salt, the sulfuric acid of derivative of fatty acid) or sulphur
The one of hydrochlorate (alkylbenzenesulfonate, alkylnaphthalene sulfonate, alkyl sulfonate, petroleum sulfonate, lignosulfonates etc.) or its
In several mixture.
In the preparation method of above-mentioned lithium ion battery ternary precursor material, in described nickel cobalt manganese salt-mixture, nickel salt is sulfur
A kind of or the most several mixture in acid nickel, nickel nitrate, nickel acetate, Nickel dichloride., cobalt salt is cobaltous sulfate, cobalt nitrate, acetic acid
A kind of or the most several mixture in cobalt, cobaltous chloride, manganese salt is the one in manganese sulfate, manganese nitrate, manganese acetate, manganese chloride
Or the most several mixture.
In the preparation method of above-mentioned lithium ion battery ternary precursor material, described M salt is soluble sulphate, nitric acid
Salt, acetate, chlorate, citrate, a kind of or the most several mixture of alkoxide.
In the preparation method of above-mentioned lithium ion battery ternary precursor material, described chelating agent is ammonia, ammonium chloride, carbon
Acid ammonium, ammonium nitrate, ammonium sulfate, ammonium acetate, EDTA, ammonium citrate, ethylenediamine, acetic acid, sodium fluoride, tartaric acid, maleic acid, succinum
A kind of or the most several mixture in acid, citric acid, malonic acid, chelating agent is 0.1-with the mol ratio of the total salt of metal
10.0。
In the preparation method of above-mentioned lithium ion battery ternary precursor material, for NixCoyMnzM1-x-y-z(OH)2Material
Material, described precipitant is a kind of or the most several mixture in sodium hydroxide, potassium hydroxide, Lithium hydrate；For
NixCoyMnzM1-x-y-zCO3Material, described precipitant is a kind of or the most several mixing in sodium carbonate, potassium carbonate, lithium carbonate
Thing；Precipitant is 0.1-4.0 with the mol ratio of the total salt of metal.
A kind of lithium ion battery positive pole material of the primary particle bulk density with interior solid, outside open structure
Material, has accumulation compactness interior solid, outside open structure for be prepared from by above-mentioned ternary precursor material and lithium source
LiNixCoyMnzM1-x-y-zO2Material.
The preparation method of a kind of above-mentioned anode material for lithium ion battery, comprises the steps: to have interior solid, outer
The lithium ion battery of the primary particle bulk density of portion's open structure with ternary precursor material and lithium source according to mol ratio 1: (1
～1.25) mix homogeneously, under pure oxygen or air atmosphere, sinter 1-45h at 500-1000 DEG C, after vibration screening, piled up
Compactness interior solid, the LiNi of outside open structurexCoyMnzM1-x-y-zO2Material.
In the preparation method of above-mentioned anode material for lithium ion battery, described lithium source is Lithium hydrate, lithium nitrate, sulphuric acid
A kind of or the most several mixture in lithium, 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 an advantage that
1, present configuration is characterised by that realizing granule has accumulation compactness interior solid, outside loose structure (figure
1).It is characterized in that the surfactant concentration by introducing in differential responses phase change, make this material granule have inside and outside
Piling up the structure that consistency is different, i.e. internal relatively outside the finest and close, outside is relatively internal the most loose, according to considering material
Chemical property and the principle of tap density, when chemical constituent value can make material body play good electrical chemical property especially
(such as x: y: z=8: 1: 1) when being high rate performance, increase the internal surfactant concentration introduced, to promote tap density；Working as
Learn (such as x: y: z=1: 1: 1) when component value can not make material body play good electrical chemical property especially high rate performance, subtract
Few internal surfactant concentration introduced, to ensure that the introducing of surfactant not appreciably affects material electrochemical performance and sends out
Wave.Component characteristics is at granule optional position chemical constituent numerical value from inside to outside consistent.
2, the material prepared of the method is used to have multiplying power after sintering and cycle performance is excellent, tap density is high feature.
3, the preparation technology of the present invention is simple, and lower cost for material is suitable to industrialized production.
Accompanying drawing explanation
Fig. 1 is particle packing consistency interior solid, outside loose schematic diagram；
Fig. 2 is that comparative example does not adds the SEM pattern after surfactant reacts 12 hours；
Fig. 3 is that embodiment adds the SEM pattern after surfactant reacts 12 hours；
Fig. 4 is that comparative example does not adds the SEM pattern after surfactant reacts 24 hours；
Fig. 5 is that embodiment adds the SEM pattern after surfactant reacts 24 hours；
Fig. 6 is that comparative example does not adds the adsorption isothermal curve test result after surfactant reacts 24 hours；
Fig. 7 is that embodiment adds the adsorption isothermal curve test result after surfactant reacts 24 hours；
Fig. 8 is the high rate performance test result of comparative example and embodiment；
Fig. 9 is that comparative example does not adds surfactant and reacts the first charge-discharge curve of material after the sintering after 24 hours；
Figure 10 is that embodiment adds surfactant and reacts the first charge-discharge curve of material after the sintering after 24 hours；
Detailed description of the invention
Below in conjunction with the accompanying drawings technical scheme is further described, but is not limited thereto, every to this
Inventive technique scheme is modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention, all should contain
In protection scope of the present invention.
Comparative example with the evaluation of material mode of embodiment is: by prepared persursor material with sintering after material carry out respectively
Particle size distribution, tap density and BET specific surface area characterize, and material after sintering is carried out electrochemistry multiplying power and first charge-discharge capacity
Performance characterization.
Comparative example 1
Preparation mol ratio is Ni: Co: Mn=8: 1: 1 and total concentration is the nickel sulfate of 2mol/L, manganese sulfate, cobaltous sulfate mixing
Metal salt solution, the chelating agent ammonia spirit of 2.8mol/L, the precipitant sodium hydroxide solution of 2mol/L.By metal salt solution,
Ammonia spirit, sodium hydroxide solution than in the reactor adding high-speed stirred, control the pH of whole reaction system with given pace
10 ± 0.3, temperature controls at 58 DEG C, after reacting 24 hours, after cleaned, the soluble impurity that is filtered to remove in material,
Material is dried, by drying material with Lithium hydrate with 1 under vacuum atmosphere∶The mixed in molar ratio of 1.05, under pure oxygen atmosphere, 900
DEG C sintering 24 hours, obtain LiNi0.73Co0.12Mn0.15O2Powder.
After tested, reaction to 12 hours persursor material specific surface areas are 2.3m2/ g, reaction was to 24 hours persursor materials
Specific surface area is 0.95m2/ g, the median D50 of persursor material are 11.2 μm, and tap density is 1.88g/cm3, after sintering
Material discharge capacity first is 196mAh/g, circulates 30 capacity retention 84%, 0.5C capacity 183mAh/g, 1C capacity
176mAh/g。
Five, by mixed metal salt a1 solution, precipitant water c1 solution, chelating agent water d1 solution, (precipitant is as hydrogen with 1: 2: 1
During oxide) or the feed rate ratio injection continuous stirring Liquid-phase reactor of 1: 1: 1 (when precipitant is carbonate), reaction condition
As follows: inert atmosphere, pH value is 6-14, constant temperature 35-85 DEG C, and the response time is t1 (0 ＜ t1 ＜ 100h)；
Six: surfactant solution b1 is added reactor in zero moment, by controlling the feed rate of a1, b1, c1, d1
Collocation so that the concentration moment of surfactant maintains the value same with liquid phase of the initial end, always adding the time of surfactant
For t2 (t2 ＜ t1,0 ＜ t2 ＜ 100h)；
Seven: when reaction was carried out to the t2 moment, suspending charging, settled by solution left standstill in reactor, the sedimentation time is t3 (0
＜ t3 ＜ 10h), after having settled, remove all supernatant dissolved with surfactant in reactor, and add isopyknic instead
Should substitute by end liquid V1, continue to feed according to the process conditions of step 5, react to after the t1 moment, prepare and there is accumulation compactness be
Interior solid, the Ni of outside open structurexCoyMnzM1-x-y-z(OH)2Or NixCoyMnzM1-x-y-zCO3Material.
Embodiment 1
Preparation mol ratio is Ni: Co: Mn=8: 1: 1 and total concentration is the nickel sulfate of 2mol/L, manganese sulfate, cobaltous sulfate metal
Saline solution, the chelating agent ammonia spirit of 2.8mol/L, the precipitant sodium hydroxide solution of 2mol/L, the dodecyl sulphur of 1mol/L
Acid sodium hydrothermal solution.By enveloping agent solution, deionized water, aqueous surfactant solution according to 1∶6∶800ml altogether is molten for the mol ratio of 1
Liquid adds in reactor, as liquid at the bottom of the reaction in zero moment；By metal salt solution, the chelating agent ammonia spirit of 2.8mol/L and
The precipitant sodium hydroxide solution of 2mol/L adds in the reactor of high-speed stirred with given pace ratio (1: 1: 2), and wherein 12
Sodium alkyl sulfonate mixed solution introduced at first 12 hours, controlled the pH of whole reaction system 10 ± 0.3, and temperature controls 58
DEG C, to react after 12 hours, suspend charging, solution left standstill in reactor is settled, the sedimentation time is 1h, after having settled, removes
All supernatant dissolved with surfactant in dereaction still, and add liquid replacement at the bottom of isopyknic reaction, continue control whole
The pH of reaction system is 10 ± 0.3, and temperature controls at 58 DEG C, reacts to after 24 hours, material is cleaned, be filtered to remove material
In soluble impurity after, obtain Ni0.8Co0.1Mn0.1(OH)2, under vacuum atmosphere, dry material, by drying material and hydrogen-oxygen
Changing the mixed in molar ratio that lithium is with 1: 1.05, under pure oxygen atmosphere, 900 DEG C sinter 24 hours, obtain LiNi0.8Co0.1Mn0.1O2Powder
End, this material granule piles up compactness interior solid, outside loose, and chemical constituent is the most consistent.
After tested, add surfactant reacting after 12 hours specific surface area is 0.52m2/ g, reacted after 24 hours
Specific surface area is 0.36m2/ g, the median D50 of this persursor material are 10 μm, and tap density is 2.2g/cm3, first after sintering
Secondary discharge capacity is 198mAh/g, circulates 30 capacity retention 81%, 0.5C capacity 185mAh/g, 1C capacity 175mAh/g.
It will be seen that after adding surfactant, the accumulation compactness of material is higher, granule after being contrasted by Fig. 2, Fig. 3
Grow more closely knit.
It will be seen that owing to latter 12 hours do not introduce surfactant after being contrasted by Fig. 4, Fig. 5, therefore from surface sweeping Electronic Speculum
The accumulation consistency not observing material surface on figure has significant change.
Being shown by the BET test result of Fig. 6, Fig. 7, after introducing surfactant, the specific surface area of material is less, with scanning
Electronic Speculum test result is coincide, and further demonstrating surfactant, that Material growth can be promoted to obtain is more densely cross-linked.
Fig. 8 test result indicate that, the introducing of surfactant can weaken the high rate performance of material to a certain extent, but
The weakening degree of high rate performance is the most inconspicuous.
In Fig. 9, Figure 10, first charge-discharge capacity comparison result shows, after introducing surfactant, and the capacity first of material
Not being significantly affected, difference of them is inconspicuous.
Embodiment 2
Preparation mol ratio is Ni: Co: Mn=8: 1: 1 and total concentration is the nickel sulfate of 2mol/L, manganese sulfate, cobaltous sulfate metal
Saline solution, the chelating agent ammonia spirit of 2.8mol/L, the precipitant sodium carbonate liquor of 2mol/L, the dodecyl sodium sulfonate of 1mol/L
Sodium hydrothermal solution.Enveloping agent solution, deionized water, aqueous surfactant solution are total to 800ml solution according to the mol ratio of 1: 6: 1
Add in reactor, as liquid at the bottom of the reaction in zero moment；By metal salt solution, the chelating agent ammonia spirit of 2.8mol/L and
The precipitant sodium carbonate liquor of 2mol/L adds in the reactor of high-speed stirred with given pace ratio (1: 1: 1), wherein dodecane
Base sodium sulfonate mixed solution introduced at first 12 hours, controlled the pH of whole reaction system 10 ± 0.3, and temperature controls at 58 DEG C,
Reacting after 12 hours, suspend charging, settled by solution left standstill in reactor, the sedimentation time is 1h, after having settled, removes anti-
All supernatant dissolved with surfactant in answering still, and add liquid replacement at the bottom of isopyknic reaction, continue to control whole reaction
The pH of system is 10 ± 0.3, and temperature controls at 58 DEG C, reacts to after 24 hours, material is cleaned, be filtered to remove in material
After soluble impurity, obtain Ni0.8Co0.1Mn0.1CO3, under vacuum atmosphere, dry material, by drying material with Lithium hydrate with 1
: the mixed in molar ratio of 1.05, under pure oxygen atmosphere, 900 DEG C sinter 24 hours, obtain LiNi0.8Co0.1Mn0.1O2Powder, this material
Material particle packing compactness interior solid, outside loose, and chemical constituent is the most consistent.
Embodiment 3
The present embodiment is with the difference of embodiment 1: precipitant is the mixture of sodium hydroxide and potassium hydroxide, the two
Mol ratio is 1: 1；Lithium source is Lithium hydrate and lithium nitrate and the mixture of lithium sulfate, Lithium hydrate, lithium nitrate, the rubbing of lithium sulfate
Your ratio is 1: 1: 2.
Embodiment 4
The present embodiment is with the difference of embodiment 1: chelating agent is the mixture of ammonia and ammonium chloride, the mol ratio of the two
Being 1: 1, M is the mixture of chromium and aluminum, and respectively presented in chromic sulfate with aluminum sulfate, the mol ratio of the two is 1: 1.
Embodiment 5
The present embodiment is with the difference of embodiment 1: surfactant is sodium lauryl sulphate and cetyl sulfonic acid
Sodium and the mixture of dodecylbenzene sodium sulfonate, sodium lauryl sulphate, sodium cetanesulfonate, dodecylbenzene sodium sulfonate
Mol ratio is 10: 1: 2.
Embodiment 6
The present embodiment is with the difference of embodiment 1: corresponding to slaine, anion is chosen for nitrate anion, i.e. nickel nitrate,
Cobalt nitrate, manganese nitrate.
Embodiment 7
The present embodiment is with the difference of embodiment 1: the mol ratio of Ni: Co: Mn is 4: 3: 3.
Embodiment 8
The present embodiment is with the difference of embodiment 1: the mol ratio of Ni: Co: Mn is 5: 2: 3.
Embodiment 9
The present embodiment is with the difference of embodiment 2: precipitant is the mixture of sodium carbonate and potassium carbonate, sodium carbonate, carbon
The mol ratio of acid potassium is 3: 1；Lithium source is Lithium hydrate and lithium nitrate and the mixture of lithium oxalate, Lithium hydrate, lithium nitrate, oxalic acid
The mol ratio of lithium is 5: 2: 1.
Embodiment 10
The present embodiment is with the difference of embodiment 2: chelating agent is the mixture of ammonia and ammonium nitrate, ammonia, ammonium nitrate
Mol ratio be 5: 1, M is the mixture of chromium and magnesium, and respectively presented in chromic nitrate and magnesium sulfate, the mol ratio of the two
It is 1: 1.
Embodiment 11
The present embodiment is with the difference of embodiment 2: surfactant is chosen for sodium lauryl sulphate and dodecyl
The mixture of sodium sulfonate, sodium lauryl sulphate is 2: 1 with the mol ratio of dodecyl sodium sulfate.
Embodiment 12
The present embodiment is with the difference of embodiment 2: corresponding to slaine, anion is chosen for chloride ion, i.e. Nickel dichloride.,
Cobaltous chloride, manganese chloride.
Embodiment 13
The present embodiment is with the difference of embodiment 2: the mol ratio of Ni: Co: Mn is 4: 3: 3.
Embodiment 14
The present embodiment is with the difference of embodiment 2: the mol ratio of Ni: Co: Mn is 5: 2: 3.
Claims (10)
1. there is a ternary precursor material for the primary particle bulk density of interior solid, outside open structure, its feature
It is that the granule of described ternary precursor material has accumulation compactness interior solid, outside open structure, i.e. building up inside tight
Density piles up compactness more than outside, and ternary precursor material is NixCoyMnzM1-x-y-z(OH)2Or NixCoyMnzM1-x-y-zCO3,
0 < x < 1,0 < y < 1,0 < z < 1, x+y+z≤1, M be Zr, Fe, Sm, Pr, Nb, Ga, Zn, Y, Mg, Al, Cr, Ca, Na, Ti, Cu, K,
One or more in Sr, Mo, Ba, Ce, Sn, Sb, La, Bi.
Before the ternary of the primary particle bulk density with interior solid, outside open structure the most according to claim 1
Drive body material, it is characterised in that in described accumulation compactness interior solid, outside open structure, the inside and outside chemical constituent of material
Identical.
Before the ternary of the primary particle bulk density with interior solid, outside open structure the most according to claim 1
Driving body material, it is characterised in that the second particle mean diameter of described ternary precursor material is 1-40 μm, tap density is 1-
4g/cm3。
4. before the ternary of the primary particle bulk density with interior solid, outside open structure described in a claim 1
Drive the preparation method of body material, it is characterised in that described method step is as follows:
One, it is 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 aqueous solution b1,0.01mol/L < B < 20 mol/L that concentration is B；
Three, be respectively configured the precipitant aqueous solution c1 that concentration is C and the complexing agent aqueous solution d1,0.01mol/L < C that concentration is D <
20 mol/L, 0.01mol/L < D < 20 mol/L；
Four, enveloping agent solution d1, deionized water, aqueous surfactant solution b1 are added continuously according to the molar ratio of 1:6:x
In stirring Liquid-phase reactor, 0.01≤x≤100, as liquid V1 at the bottom of the reaction in zero moment；
Five, mixed salt solution a1, precipitant aqueous solution c1, complexing agent aqueous solution d1 is fast with the charging of 1:2:1 or 1:1:1
Rate is than injecting continuous stirring Liquid-phase reactor, and reaction condition is as follows: inert atmosphere, and 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, taken by the feed rate controlling a1, b1, c1, d1
Join so that the concentration moment of surfactant maintain with liquid phase of the initial end with value, total interpolation time of surfactant is
T2, t2 < t1,0 < t2 < 100h；
Seven: when reaction was carried out to the t2 moment, suspending charging, settled by solution left standstill in reactor, the sedimentation time is t3,0 < t3 <
10h, after having settled, removes the interior supernatant dissolved with surfactant of reactor, and adds and the isopyknic reaction of supernatant
End liquid V1 substitutes, and continues to feed according to the process conditions of step 5, reacts to after the t1 moment, prepares that to have accumulation compactness be interior
Portion is fine and close, the Ni of outside open structurexCoyMnzM1-x-y-z(OH)2Or NixCoyMnzM1-x-y-zCO3Material.
Before the ternary of the primary particle bulk density with interior solid, outside open structure the most according to claim 4
Drive the preparation method of body material, it is characterised in that described NixCoyMnzM1-x-y-z(OH)2Or NixCoyMnzM1-x-y-zCO3Material
Chemical constituent is consistent in granule optional position.
Before the ternary of the primary particle bulk density with interior solid, outside open structure the most according to claim 4
Drive the preparation method of body material, it is characterised in that described surfactant is sulfuric acid and/or sulfonate, wherein: sulfuric ester
Salt is in the sulfuric acid of fatty alcohol sulphuric acid, secondary alkyl sulfate, polyoxyethylene alkyl ether sulfate salt, derivative of fatty acid
A kind of or the most several mixture, sulfonate is alkylbenzenesulfonate, alkylnaphthalene sulfonate, alkyl sulfonate, mahogany acid
A kind of or the most several mixture in salt, lignosulfonates；Described nickel salt is nickel sulfate, nickel nitrate, nickel acetate, chlorination
A kind of or the most several mixture in nickel, cobalt salt is the one in cobaltous sulfate, cobalt nitrate, cobaltous acetate, cobaltous chloride or wherein
Several mixture, manganese salt is a kind of or the most several mixture in manganese sulfate, manganese nitrate, manganese acetate, manganese chloride, M salt
For soluble sulphate, nitrate, acetate, chlorate, citrate, a kind of or the most several mixture of alkoxide；Institute
State chelating agent be ammonia, ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium acetate, EDTA, ammonium citrate, ethylenediamine, acetic acid,
A kind of or the most several mixture in sodium fluoride, tartaric acid, maleic acid, succinic acid, citric acid, malonic acid；For
NixCoyMnzM1-x-y-z(OH)2Material, described precipitant is a kind of or the most several in sodium hydroxide, potassium hydroxide, Lithium hydrate
Kind mixture, mixed salt solution a1, precipitant aqueous solution c1, complexing agent aqueous solution d1 feed rate ratio for 1:2:1；
For NixCoyMnzM1-x-y-zCO3Material, described precipitant is a kind of or the most several in sodium carbonate, potassium carbonate, lithium carbonate
Mixture, mixed salt solution a1, precipitant aqueous solution c1, complexing agent aqueous solution d1 feed rate than for 1:1:1.
Before the ternary of the primary particle bulk density with interior solid, outside open structure the most according to claim 4
Drive the preparation method of body material, it is characterised in that chelating agent described in step 5 is 0.1-10.0 with the mol ratio of the total salt of metal,
Precipitant is 0.1-4.0 with the mol ratio of the total salt of metal.
8. there is an anode material for lithium ion battery for the primary particle bulk density of interior solid, outside open structure,
It is characterized in that described positive electrode is to be had accumulation by ternary precursor material described in claim 1 with lithium source is prepared from
Compactness is interior solid, the LiNi of outside open structurexCoyMnzM1-x-y-zO2Material.
9. the lithium ion of the primary particle bulk density with interior solid, outside open structure described in a claim 8
The preparation method of positive electrode for battery material, it is characterised in that described method step is as follows: will have interior solid, outside loose knot
The lithium ion battery of the primary particle bulk density of structure with ternary precursor material and lithium source according to mol ratio 1:(1～1.25) mixed
Close uniformly, under pure oxygen or air atmosphere, sinter 1-45h at 500-1000 DEG C, after vibration screening, obtain interior solid, outside
The LiNi of open structurexCoyMnzM1-x-y-zO2Material.
The lithium ion of the primary particle bulk density with interior solid, outside open structure the most according to claim 9
The preparation method of positive electrode for battery material, it is characterised in that described lithium source is Lithium hydrate, lithium nitrate, lithium sulfate, lithium chloride, fluorine
Change a kind of or the most several mixture in lithium, lithium oxalate, lithium phosphate, lithium hydrogen phosphate, lithium carbonate.
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| CN105355907B (en) * | 2015-12-10 | 2018-03-30 | 哈尔滨工业大学 | Positive electrode and preparation method prepared by lithium metal oxide persursor material and the material with " annual ring " formula structure |
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