CN106340629A - Modification method of lithium cobalt oxide material - Google Patents
Modification method of lithium cobalt oxide material Download PDFInfo
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- CN106340629A CN106340629A CN201610978945.XA CN201610978945A CN106340629A CN 106340629 A CN106340629 A CN 106340629A CN 201610978945 A CN201610978945 A CN 201610978945A CN 106340629 A CN106340629 A CN 106340629A
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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
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- H01M4/362—Composites
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- H—ELECTRICITY
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- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- 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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Abstract
The invention provides a modification method of a lithium cobalt oxide material. The modification method comprises the following steps that firstly, a cobalt source, a complexing agent, an alkali liquor and an antioxidant are mixed for reaction, then an aluminum source solution is added for in-situ coating, and then a coated precursor is obtained; then, the coated precursor obtained in the step is calcined with a lithium source to obtain a coated and modified lithium cobalt oxide material. The coating is performed in the precursor preparing process based on a liquid phase, namely the coating is achieved on the surface of the precursor, the obtained coated precursor is mixed and calcined with the lithium source to obtain the uniformly coated lithium cobalt oxide material. In addition, the Co(OH)2 precursor is adopted, and uniform Al(OH)3 coating is directly achieved based on the preparation. Furthermore, the whole process is simple, no process is added, the costs are low, and the modification method is suitable for large-scale production and application.
Description
Technical field
The present invention relates to technical field of lithium ion battery electrode, it is related to a kind of method of modifying of cobalt acid lithium material, especially
It is related to a kind of coating modification method of cobalt acid lithium material.
Background technology
Lithium battery has that operating voltage is high, specific energy is high, has extended cycle life, lightweight, white electric discharge less, memory-less effect with
Cost performance ratio, it has also become the master of the field such as high power electric vehicle, artificial satellite, Aero-Space rechargeable type power supply
Want selecting object.Therefore lithium ion battery and its associated materials become the study hotspot of scientific research personnel.Positive electrode is lithium ion
One of battery critical material, decides the performance of lithium ion battery.And current limiting lithium ion electrokinetic cell energy density, power
The maximum bottleneck of density, cycle life and security is positive electrode technology.
Cobalt acid lithium (licoo2) as anode material for lithium-ion batteries pioneer, be in lithium ion battery a kind of preferably just
Pole material, has the advantages that operating voltage is high, electric discharge is steady, specific energy is high and good cycle, its chemical property is superior,
As every circulation one cycle capacity average attenuation is less than 0.05%, first discharge specific capacity is more than 135mah/g, 3.6v initial discharge
Platform ratio is more than 85% etc.；Processing characteristics is excellent, and such as tap density is big, is favorably improved battery volume and capacity ratio, product
Stable performance, uniformity is good etc..Thus cobalt acid lithium is suitable for big flow electric discharge and the embedded and abjection of lithium ion, in lithium-ion electric
Obtain in pond taking the lead in using.
Just because of cobalt acid lithium, there is the advantages such as simple production process and stable electrochemical property, it has also become be to count not at present
How to be practically applicable to produce, realized the anode material for lithium-ion batteries of commercialization, have passed through the development of 30 years, cobalt acid lithium is produced in electronics
More than 80% market has been occupied in product lithium ion battery.Especially in small consumer field of batteries, there is important application,
Due to developing rapidly of consumer electronics product market, cobalt acid lithium is also the maximum material of sales volume accounting in anode material of lithium battery
Material.
But cobalt acid lithium still has many shortcomings, as cycle performance, cobalt resource is rare, price is high and pollutes ring
Border, and it is unable to high rate charge-discharge, uniformity is bad etc., so from exploitation in 1980 so far, between always not having in industry
Broke the exploration to its performance and modification, among these, because cobalt acid lithium material is monodisperse spherical particle, with respect to random
Particle then, the spheric granules surface of rule is easier to coat, therefore, and coating modification cobalt acid lithium material, surface is carried out to it
Modify and improve combination property, the always main method of modifying of cobalt acid lithium material further.
But due to the cobalt acid lithium material defect of itself, the method for existing coating modification, still exist and be difficult to uniformly
Cladding, high cost and the requirement that high-multiplying power discharge can not be met.
Therefore, how to find a kind of method of modifying of cobalt acid lithium material preferably, overcome drawbacks described above, it has also become in the industry
One of focus of numerous research and development type manufacturing enterprises extensive concern.
Content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of method of modifying of cobalt acid lithium material, this
The coating modification method of the cobalt acid lithium material of bright offer, cobalt acid lithium material itself has higher density, is capable of uniformly wrapping
Cover, and adapt to the requirement of high power charging-discharging.Meanwhile, the present invention provide preparation method process is simple, low cost it is adaptable to
Large-scale production and application.
The invention provides a kind of method of modifying of cobalt acid lithium material, comprise the following steps:
1) by after cobalt source, complexing agent, alkali lye and antioxidant hybrid reaction, after adding silicon source solution in-stiu coating, obtain
Presoma to after cladding；
2), after the presoma after the cladding obtaining above-mentioned steps is calcined with lithium source, obtain the cobalt acid lithium material of coating modification
Material.
Preferably, described cobalt source includes in anhydrous cobaltous sulfate, cobalt sulfate hydrate, waterless cobaltous chloride and hydrated cobalt chloride
Plant or multiple；
Source of aluminium includes one of anhydrous slufuric acid aluminium, hydrazine aluminum sulfate, anhydrous Aluminum chloride and aluminium chlorohydrate or many
Kind；
Described lithium source is included in lithium carbonate, anhydrous lithium hydroxide, hydronium(ion) lithia, anhydrous lithium acetate and hydration lithium acetate
One or more.
Preferably, described alkali lye includes sodium hydroxide solution and/or potassium hydroxide solution；
Described complexing agent includes ammoniacal liquor and/or ammonium chloride；
Described antioxidant includes one or more of hydrazine hydrate, ascorbic acid and glucose.
Preferably, the mol ratio of described cobalt source and alkali is 1:(2.15～2.4)；
The mol ratio of described antioxidant and described cobalt source is 1:(0.05～0.5)；
In described complexing agent, ammonium ion and the mol ratio of cobalt ions in described cobalt source are 1:(0.5～1)；
In described cobalt source, cobalt ions and aluminum ions mol ratio in silicon source are 1:(0.01～0.1)；
In described cobalt source, cobalt ions and the mol ratio of lithium ion in lithium source are 1:(1.02～1.07).
Preferably, the temperature of described calcining is 450～1000 DEG C；
The time of described calcining is 12～18h.
Preferably, described cobalt source is cobalt source solution；The concentration of described cobalt source solution is 50～200g/l；
The concentration of described alkali lye is 30～80g/l.
Preferably, described step 1) particularly as follows:
11) complexing agent, alkali lye and antioxidant are first mixed, then after dropping cobalt source solution hybrid reaction, more slowly add
Precursor solution after entering silicon source solution in-stiu coating, after being coated；
12) precursor solution after above-mentioned cladding is post-processed, the presoma after being coated.
Preferably, the time of described hybrid reaction is 0.5～1h；
The temperature of described hybrid reaction is 50～60 DEG C；
The time of described in-stiu coating is 1～2h.
Preferably, the speed of described dropping is 300～500ml/h；
Described be incorporated slowly as instill；
The speed of described instillation is 50～150ml/h.
Preferably, described post processing includes one or more of filtering, be dried, wash, grind and being heat-treated.
The invention provides a kind of method of modifying of cobalt acid lithium material, comprise the following steps, first by cobalt source, complexing agent,
Presoma after alkali lye and antioxidant hybrid reaction, after adding silicon source solution in-stiu coating, after being coated；Then will be upper
After stating the presoma after the cladding that step obtains and lithium source calcining, obtain the cobalt acid lithium material of coating modification.With prior art phase
It is difficult to be uniformly dispersed for cobalt acid lithium than, the present invention it is difficult to realize uniform cladding, and then affect the lacking of chemical property of material
Fall into, and the later stage increased the process of cobalt acid lithium dispersion and subsequent heat treatment, increases the problem of cost.The present invention is in liquid phase system
Coated during standby presoma, realized cladding on the surface of presoma, obtain is the presoma after coating, then will
The cobalt acid lithium material that this presoma and lithium source mixed calcining are uniformly coated；And the present invention uses co (oh)2Forerunner
Body, and it is directly realized by uniform al (oh) on the basis of its preparation3Cladding, also effectively solve existing with co3o4For forerunner
Body adopts solid phase method calcining synthesis, causes material particle size big, electrode density low it is impossible to meet lacking of the requirement of high power charging-discharging
Fall into.
The liquid phase preparation method of the high-density lithium cobalt oxide presoma that the present invention adopts, is forged due to being mixed with lithium source in presoma
During burning, play a part template, thus highdensity cobalt acid lithium material is obtained using this high density forerunner's physical efficiency.With
When integrated artistic simple, do not increase flow process, low cost is it is adaptable to large-scale production and application.Test result indicate that, the present invention provides
The method of coating modification enable the uniform cladding of cobalt acid lithium, and coating modification cobalt acid lithium material has preferable cyclicity
Energy and high rate performance, under the conditions of 1c, after 100 circulations, capacity attenuation is minimum only has 4%, under the conditions of 2c, 100 circulations
Capability retention can reach 95.2% afterwards；And the loose shape density of powdered modified material is up to 1.97g/cm3, tap density height
Reach 2.85g/cm3.
Brief description
Fig. 1 is the process flow diagram of the highdensity cobalt acid lithium covering material of preparation in embodiment 1.
Specific embodiment
In order to further appreciate that the present invention, with reference to embodiment, the preferred embodiments of the invention are described, but
It is it should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention rather than to patent requirements of the present invention
Limit.
The all raw materials of the present invention, originate to it and are not particularly limited, commercially buying or according to people in the art
Conventional method preparation known to member.
The all raw materials of the present invention, are not particularly limited to its purity, present invention preferably employs analyzing pure or lithium ion battery
The conventional purity in field.
The invention provides a kind of method of modifying of cobalt acid lithium material, comprise the following steps:
1) by after cobalt source, complexing agent, alkali lye and antioxidant hybrid reaction, after adding silicon source solution in-stiu coating, obtain
Presoma to after cladding；
2), after the presoma after the cladding obtaining above-mentioned steps is calcined with lithium source, obtain the cobalt acid lithium material of coating modification
Material.
The present invention wraps in situ by after cobalt source, complexing agent, alkali lye and antioxidant hybrid reaction, adding silicon source solution first
Presoma after covering, after being coated.
The present invention is not particularly limited to described cobalt source, with well known to those skilled in the art for preparing cobalt acid lithium material
Cobalt source compound, those skilled in the art can carry out according to practical condition, cladding situation and properties of product
Select, cobalt source of the present invention preferably includes in anhydrous cobaltous sulfate, cobalt sulfate hydrate, waterless cobaltous chloride and hydrated cobalt chloride
Plant or multiple, more preferably anhydrous cobaltous sulfate, cobalt sulfate hydrate, waterless cobaltous chloride or hydrated cobalt chloride, be more preferably hydrated sulphur
Sour cobalt or hydrated cobalt chloride, most preferably Cobalt monosulfate heptahydrate, i.e. coso4·7h2o.The present invention is improve reaction further equal
Even property and stability, described cobalt source is preferably cobalt source solution.The present invention is not particularly limited to the concentration of described cobalt source solution, with
The normal concentration of preparation cobalt acid lithium material well known to those skilled in the art, those skilled in the art can be according to actual raw
Product situation, cladding situation and properties of product are selected, and the concentration of cobalt source solution of the present invention is preferably 50～200g/l,
More preferably 75～175g/l, most preferably 100～150g/l.
The present invention is not particularly limited to described alkali lye, with well known to those skilled in the art for preparing cobalt acid lithium material
Alkali lye, those skilled in the art can be selected according to practical condition, cladding situation and properties of product, this
Invent described alkali lye and preferably include sodium hydroxide solution and/or potassium hydroxide solution, more preferably sodium hydroxide solution or hydrogen-oxygen
Change potassium solution, most preferably sodium hydroxide solution.The present invention is not particularly limited to the addition of described alkali lye, with this area skill
The amount of being routinely added to known to art personnel, those skilled in the art can be according to practical condition, cladding situation and product
Moral character can be selected, and the mol ratio of cobalt source of the present invention and alkali is preferably 1:(2.15～2.4), more preferably 1:(2.2～
2.35), most preferably 1:(2.25～2.3).The present invention is not particularly limited to the concentration of described alkali lye, with people in the art
The normal concentration of the alkali lye known to member, those skilled in the art can be according to practical condition, cladding situation and product
Moral character can be selected, and the concentration of alkali lye of the present invention is preferably 30～80g/l, more preferably 40～70g/l, most preferably
50～60g/l.
The present invention is not particularly limited to described antioxidant, with antioxidant well known to those skilled in the art,
Those skilled in the art can be selected according to practical condition, cladding situation and properties of product, of the present invention anti-
Oxidant preferably includes one or more of hydrazine hydrate, ascorbic acid and glucose, more preferably hydrazine hydrate, ascorbic acid or
Glucose, most preferably hydrazine hydrate.The present invention is not particularly limited to the addition of described antioxidant, with people in the art
The amount of being routinely added to known to member, those skilled in the art can be according to practical condition, cladding situation and product
Can be selected, the mol ratio of antioxidant of the present invention and described cobalt source is preferably 1:(0.05～0.5), more preferably 1:
(0.1～0.4), most preferably 1:(0.2～0.3).
The present invention is not particularly limited to described complexing agent, and those skilled in the art can be according to practical condition, bag
Cover situation and properties of product are selected, complexing agent of the present invention preferably includes ammoniacal liquor and/or ammonium chloride, more preferably ammonia
Water or ammonium chloride, most preferably ammoniacal liquor.The present invention is not particularly limited to the addition of described complexing agent, with people in the art
The amount of being routinely added to known to member, those skilled in the art can be according to practical condition, cladding situation and product
Can be selected, in ammonium ion and described cobalt source in complexing agent of the present invention the mol ratio of cobalt ions be preferably 1:(0.5～
1), more preferably 1:(0.6～0.9), most preferably 1:(0.7～0.8).
The present invention is not particularly limited to source of aluminium, with well known to those skilled in the art for preparing cobalt acid lithium material
Aluminum source compound, those skilled in the art can carry out according to practical condition, cladding situation and properties of product
Select, silicon source of the present invention preferably includes in anhydrous slufuric acid aluminium, hydrazine aluminum sulfate, anhydrous Aluminum chloride and aluminium chlorohydrate
Plant or multiple, more preferably anhydrous slufuric acid aluminium, hydrazine aluminum sulfate, anhydrous Aluminum chloride and aluminium chlorohydrate, most preferably anhydrous sulphur
Sour aluminium, i.e. al2(so4)3；The present invention is not particularly limited to the addition of source of aluminium, with system well known to those skilled in the art
The amount of being routinely added to of standby cobalt acid lithium material, those skilled in the art can according to practical condition, coat situation and
Properties of product are selected, and in cobalt ions and source of aluminium in cobalt source of the present invention, aluminum ions mol ratio is preferably 1:
(0.01～0.1), more preferably 1:(0.03～0.08), most preferably 1:(0.05～0.06).
The present invention is uniformity and the stability ensureing reaction, improves the effect of hybrid reaction and cladding further, described
Step 1) preferably particularly as follows:
11) alkali lye and antioxidant are first mixed, then after dropping cobalt source solution hybrid reaction, be slow added into silicon source molten
Precursor solution after liquid in-stiu coating, after being coated；
12) precursor solution after above-mentioned cladding is post-processed, the presoma after being coated.
The present invention is not particularly limited to the mode of described mixing and condition, with mixing well known to those skilled in the art
Mode and condition, those skilled in the art can be selected according to practical condition, cladding situation and properties of product
Select, the mode of mixing of the present invention is preferably and uniformly mixes, and more preferably uniformly mixes under conditions of water-bath；Described stirring
Speed be preferably 300～400r/min, more preferably 320～380r/min, most preferably 340～360r/min.The present invention
The speed of described dropping is not particularly limited, those skilled in the art can according to practical condition, cladding situation and
Properties of product are selected and are adjusted, the speed preferably 300～500ml/h of dropping of the present invention, more preferably 350～
450ml/h, most preferably 380～430ml/h.
The present invention is not particularly limited to the condition of described hybrid reaction, with reaction condition well known to those skilled in the art
, those skilled in the art can be selected according to practical condition, cladding situation and properties of product, institute of the present invention
The time stating hybrid reaction is preferably 0.5～1h, more preferably 0.6～0.9h, most preferably 0.7～0.8h；Described mixing is anti-
The temperature answered is preferably 50～60 DEG C, more preferably 52～58 DEG C, most preferably 54～56 DEG C.The present invention is further preferably in described mixing
In course of reaction, remain alkalescence condition, specific ph value can preferably greater than be equal to 10, or more than or equal to 11, or greatly
In equal to 12.
The present invention is not particularly limited to the described mode being slowly added to, and those skilled in the art can be according to actual production
Situation, cladding situation and properties of product are selected and are adjusted, and of the present invention are slowly added to preferably instill；The present invention couple
The speed of described instillation is not particularly limited, and those skilled in the art can be according to practical condition, cladding situation and product
Moral character can be selected and be adjusted, and the speed of instillation of the present invention is preferably 50～150ml/h, more preferably 70～130ml/
H, most preferably 90～110ml/h.
The present invention is not particularly limited to the condition of described in-stiu coating, and those skilled in the art can be according to actual production
Situation, cladding situation and properties of product are selected, and the time of in-stiu coating of the present invention is preferably 1～2h, more preferably
For 1.2～1.8h, most preferably 1.4～1.6h.Above-mentioned steps 11 of the present invention) in all preferably carry out in a water bath.
Above-mentioned steps of the present invention coated after precursor solution (al2o3Cladding cobalt acid lithium presoma) after, then after carrying out
Process, the presoma after being coated.
The present invention is not particularly limited to the mode of described post processing and condition, with rear place well known to those skilled in the art
Reason mode and condition, those skilled in the art can be carried out according to practical condition, cladding situation and properties of product
Select and adjust, the mode of post processing of the present invention be preferably filter, be dried, washing, grind and one of heat treatment or
Multiple, more preferably carry out successively filtering, be dried, wash, grind and being heat-treated, be most specifically preferably successively by the colloid obtaining
Solution carries out suction filtration, drying, washing, secondary filter, ball milling and heat treatment.
After presoma after the cladding that above-mentioned steps are finally obtained by the present invention is calcined with lithium source, obtain the cobalt of coating modification
Sour lithium material.
The present invention is not particularly limited to described lithium source, with well known to those skilled in the art for preparing cobalt acid lithium material
Li source compound, those skilled in the art can carry out according to practical condition, cladding situation and properties of product
Select, lithium source of the present invention preferably includes lithium carbonate, anhydrous lithium hydroxide, hydronium(ion) lithia, anhydrous lithium acetate and hydration
One or more of lithium acetate, more preferably lithium carbonate, anhydrous lithium hydroxide, hydronium(ion) lithia, anhydrous lithium acetate or water
Close lithium acetate, more preferably lithium carbonate, Lithium hydroxide monohydrate (lioh h2Or Lithium acetate dihydrate (ch o)3cooli·2h2O),
It is preferably lithium carbonate, i.e. li2co3.The present invention is not particularly limited to the addition of described lithium source, ripe with those skilled in the art
The amount of being routinely added to of the Li source compound of preparation cobalt acid lithium material known, those skilled in the art can be according to actual production
Situation, cladding situation and properties of product are selected, the mol ratio of lithium ion in cobalt ions and described lithium source in described cobalt source
It is preferably 1:(1.02～1.07), more preferably 1:(1.03～1.06), most preferably 1:(1.04～1.05).
The present invention is not particularly limited to the mode of described calcining and condition, with calcining side well known to those skilled in the art
Formula and condition, those skilled in the art can be selected according to practical condition, cladding situation and properties of product
And adjustment, preferably 450～1000 DEG C of the temperature of calcining of the present invention, more preferably 550～900 DEG C, most preferably 650～
800℃；The time of described calcining is preferably 12～18h, more preferably 13～17h, most preferably 14～16h；Described calcining
Curve calcines 4.5～7.5h at being preferably 450～550 DEG C, calcines 7.5～10.5h at 800～1000 DEG C.
Above-mentioned steps of the present invention are prepared for a kind of cobalt acid lithium material of modification, i.e. a kind of high density al2o3Cladding cobalt acid lithium material
Material.The present invention is coated during liquid phase prepares presoma, realizes cladding on the surface of presoma, and obtain is bag
Presoma after covering, then this presoma and lithium source mixed calcining are obtained al2o3The uniformly cobalt acid lithium material of cladding.And this
Bright use co (oh)2Presoma, and it is directly realized by uniform al (oh) on the basis of its preparation3Cladding.The present invention adopts
The liquid phase preparation method of high-density lithium cobalt oxide presoma, due to, during presoma with lithium source mixed calcining, playing template
Effect, thus highdensity cobalt acid lithium material is obtained using this high density forerunner's physical efficiency.
The method of modifying that the present invention provides, is evenly coated, it is possible to increase the stability of product, and then realizes excellent electrification
Learn performance；And presoma cladding can suppress the growing up of cobalt acid lithium crystal in follow-up solid-phase sintering by steric effect,
And short grained cobalt acid lithium can guarantee that the electrode density of battery, adapt to the requirement of the high power charging-discharging of 3c～4c, and adopt
co(oh)2Do forerunner's physical efficiency and obtain highdensity licoo2Material, integrated artistic is simple simultaneously, does not increase flow process, low cost, fits
For large-scale production and application.Test result indicate that, the method for the coating modification that the present invention provides enables the uniform of cobalt acid lithium
Cladding, and coating modification cobalt acid lithium material has preferable cycle performance and high rate performance, circulates through 100 times under the conditions of 1c
Capacity attenuation minimum only 4% afterwards, under the conditions of 2c, after 100 circulations, capability retention can reach 95.2%；And powder
Material modified loose shape density is up to 1.97g/cm3, tap density is up to 2.85g/cm3.
In order to further illustrate the present invention, the modification to a kind of cobalt acid lithium material that the present invention provides with reference to embodiments
Method is described in detail but it is to be understood that these embodiments are to be implemented under premised on technical solution of the present invention,
Give detailed embodiment and specific operating process, simply for further illustrating the features and advantages of the present invention, and not
It is limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following embodiments.
Embodiment 1
Ratio coso by the amount of material4.7h2O:naoh:al2(so4)3=1:2.3:0.008 weighs material.Weigh 0.2mol
Coso4.7h2O, is dissolved in 1l distilled water, is made into the cobalt sulfate solution of 56g/l.The aluminum sulfate weighing 0.008mol is dissolved in
In the distilled water of 100ml, it is configured to the solution of 27.36g/l, stand-by.Weigh 0.46mol NaOH, be dissolved in 0.5l distilled water
In, it is configured to the naoh solution of 36.8g/l.
Add sodium hydroxide solution and 15ml ammoniacal liquor to be bottom liquid, add hydrazine hydrate 50ml, under the conditions of 55 DEG C of stirring in water bath,
Adjust mixing speed 300r/min, cobalt sulfate solution is instilled with 500ml/h, maintain ph ＞ 12 in the process.Treat after dripping
After reaction 1h, aluminum sulfate solution is dripped with 100ml/h flow velocity, after fully reacting with excessive naoh.The colloid that reaction is obtained
Suction filtration, drying, washing, secondary filter and secondary ball milling and heat treatment, finally obtain highdensity al2o3Before the cobalt acid lithium of cladding
Drive body.By the ratio 1.03 of the amount of li:co material, with li2co3Calcining (calcinating system: 480 DEG C～6h～900 DEG C～9h) obtains height
The cobalt acid lithium covering material of density, i.e. al2o3The licoo of cladding2Material.
Referring to Fig. 1, Fig. 1 is the process flow diagram of the highdensity cobalt acid lithium covering material of preparation in embodiment 1.
Button cell is fabricated to the cobalt acid lithium material of the coating modification of the embodiment of the present invention 1 preparation, carries out performance detection,
Result shows, under the conditions of 1c, after 100 circulations, capacity attenuation only has 4%, and its capability retention is higher than significantly uncoated
75.3%, this show the present invention provide coating modification method hence it is evident that improving the stable circulation performance of cobalt acid lithium material,
This shows al2o3Define uniform solid solution with cobalt acid lithium, decrease the directly contact of cobalt acid lithium and electrolyte.
Under the conditions of 2c, its first discharge specific capacity is 165.2mah/g, and after 100 circulations, capability retention is
95.2% it will be apparent that be higher than uncoated cobalt acid lithium (first discharge specific capacity 130mah/g, capability retention after 100 circulations
55.2%).
This shows the method for the coating modification that the present invention provides, and carries out al2o3After coating modification, the capacity of cobalt acid lithium material
Can significantly improve with cyclical stability, there is extraordinary high rate performance.
And, the loose shape density of the cobalt acid lithium powder of the embodiment of the present invention 1 preparation is up to 1.97g/cm3, tap density height
Reach 2.85g/cm3, far above general cobalt acid lithium battery material (loose shape density: 1.62g/cm3, tap density 2.5g/cm3.)
Embodiment 2
Ratio coso by the amount of material4.7h2O:naoh:al2(so4)3=1:2.3:0.004 weighs material, according to embodiment
1 mode is coated.Obtain 0.4% al2o3Cladding cobalt acid lithium, its loose shape density is up to 1.85cm3, tap density is up to
2.62m3, capacity attenuation about 12% after circulating through 100 times under the conditions of 1c.Under the conditions of 2c, first discharge specific capacity is 175.2mah/
G, after 100 circulations, capability retention is 65.3%.
Embodiment 3
Ratio coso by the amount of material4.7h2O:naoh:al2(so4)3=1:2.3:0.006 weighs material, according to embodiment
1 mode is coated.Obtain 0.6% al2o3Cladding cobalt acid lithium, its loose shape density is up to 1.92cm3, tap density is up to
2.76m3, capacity attenuation about 7% after circulating through 100 times under the conditions of 1c；Under the conditions of 2c, first discharge specific capacity is 168.1mah/g,
After 100 circulations, capability retention is 75.7%.
Embodiment 4
Ratio coso by the amount of material4.7h2O:naoh:al2(so4)3=1:2.3:0.01 weighs material, according to embodiment 1
Mode coated.Obtain 1% al2o3Cladding cobalt acid lithium, its loose shape density is up to 1.93cm3, tap density is up to
2.78m3, capacity attenuation about 4.6% after circulating through 100 times under the conditions of 1c；Under the conditions of 2c, first discharge specific capacity is
165.4mah/g, after 100 circulations, capability retention is 94.6%.
Embodiment 5
Ratio coso by the amount of material4.7h2O:naoh:al2(so4)3=1:2.3:0.012 weighs material, according to embodiment
1 mode is coated.Obtain 1.2% al2o3Cladding cobalt acid lithium, its loose shape density is up to 1.95cm3, tap density is up to
2.82m3, capacity attenuation about 4.2% after circulating through 100 times under the conditions of 1c；Under the conditions of 2c, its first discharge specific capacity is
160.2mah/g, after 100 circulations, capability retention is 89.6%.
Above a kind of method of modifying of cobalt acid lithium material that the present invention provides is described in detail, used herein
Specific case is set forth to the principle of the present invention and embodiment, and the explanation of above example is only intended to help understand
The method of the present invention and its core concept, including best mode, and also make any person skilled in the art real
Trample the present invention, including manufacture with using any device or system, and the method implementing any combination.It should be pointed out that for this skill
For the those of ordinary skill in art field, under the premise without departing from the principles of the invention, some changing can also be carried out to the present invention
Enter and modify, these improve and modify and also fall in the protection domain of the claims in the present invention.The scope of patent protection of the present invention
Be defined by the claims, and may include those skilled in the art it is conceivable that other embodiment.If these other realities
Apply example and there is the structural element being not different from claim character express, or if they include the word with claim
The equivalent structural elements of statement no essence difference, then these other embodiments also should comprise within the scope of the claims.
Claims (10)
1. a kind of method of modifying of cobalt acid lithium material is it is characterised in that comprise the following steps:
1) by after cobalt source, complexing agent, alkali lye and antioxidant hybrid reaction, after adding silicon source solution in-stiu coating, wrapped
Presoma after covering；
2), after the presoma after the cladding obtaining above-mentioned steps is calcined with lithium source, obtain the cobalt acid lithium material of coating modification.
2. method of modifying according to claim 1 is it is characterised in that described cobalt source includes anhydrous cobaltous sulfate, hydrated sulfuric acid
One or more of cobalt, waterless cobaltous chloride and hydrated cobalt chloride；
Source of aluminium includes one or more of anhydrous slufuric acid aluminium, hydrazine aluminum sulfate, anhydrous Aluminum chloride and aluminium chlorohydrate；
Described lithium source includes in lithium carbonate, anhydrous lithium hydroxide, hydronium(ion) lithia, anhydrous lithium acetate and hydration lithium acetate
Plant or multiple.
3. method of modifying according to claim 1 is it is characterised in that described alkali lye includes sodium hydroxide solution and/or hydrogen
Potassium oxide solution；
Described complexing agent includes ammoniacal liquor and/or ammonium chloride；
Described antioxidant includes one or more of hydrazine hydrate, ascorbic acid and glucose.
4. method of modifying according to claim 1 is it is characterised in that the mol ratio of described cobalt source and alkali is 1: (2.15～
2.4)；
The mol ratio of described antioxidant and described cobalt source is 1:(0.05～0.5)；
In described complexing agent, ammonium ion and the mol ratio of cobalt ions in described cobalt source are 1:(0.5～1)；
In described cobalt source, cobalt ions and aluminum ions mol ratio in silicon source are 1: (0.01～0.1)；
In described cobalt source, cobalt ions and the mol ratio of lithium ion in lithium source are 1: (1.02～1.07).
5. method of modifying according to claim 1 is it is characterised in that the temperature of described calcining is 450～1000 DEG C；
The time of described calcining is 12～18h.
6. the method for modifying according to Claims 1 to 5 any one is it is characterised in that described cobalt source is cobalt source solution；Institute
The concentration stating cobalt source solution is 50～200g/l；
The concentration of described alkali lye is 30～80g/l.
7. method of modifying according to claim 6 is it is characterised in that described step 1) particularly as follows:
11) complexing agent, alkali lye and antioxidant are first mixed, then after dropping cobalt source solution hybrid reaction, be slow added into aluminium
Precursor solution after the solution in-stiu coating of source, after being coated；
12) precursor solution after above-mentioned cladding is post-processed, the presoma after being coated.
8. method of modifying according to claim 6 is it is characterised in that the time of described hybrid reaction is 0.5～1h；
The temperature of described hybrid reaction is 50～60 DEG C；
The time of described in-stiu coating is 1～2h.
9. method of modifying according to claim 6 is it is characterised in that the speed of described dropping is 300～500ml/h；
Described be incorporated slowly as instill；
The speed of described instillation is 50～150ml/h.
10. method of modifying according to claim 6 is it is characterised in that described post processing includes filtering, is dried, washes, grinding
One or more of mill and heat treatment.
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