CN107342408A - Improve spherical doping Co3O4The method of yield and application - Google Patents
Improve spherical doping Co3O4The method of yield and application Download PDFInfo
- Publication number
- CN107342408A CN107342408A CN201710499182.5A CN201710499182A CN107342408A CN 107342408 A CN107342408 A CN 107342408A CN 201710499182 A CN201710499182 A CN 201710499182A CN 107342408 A CN107342408 A CN 107342408A
- Authority
- CN
- China
- Prior art keywords
- yield
- doping
- reaction
- spherical
- spherical doping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
Abstract
The present invention relates to cobaltosic oxide technical field of material, specifically discloses a kind of spherical doping Co of raising3O4The method of yield.This method comprises at least following steps：Cobalt salt solution, the enveloping agent solution for being complexed doped chemical ion, precipitant solution and air cocurrent are added in reaction unit and reacted；It is 60~90 DEG C to keep reaction temperature, keeps pH=9.0~11.0 of reaction mixture in the reaction unit.Present invention cobalt salt, doped chemical ion is separately formulated, the final spherical doping Co of acquisition3O4With yield is high, particle is small, epigranular is controllable, good sphericity, the features such as regular appearance, the inventive method is adapted to industrialization to mass produce spherical doping Co3O4。
Description
Technical field
The present invention relates to cobaltosic oxide technical field of material, more particularly to a kind of spherical doping Co of raising3O4Yield
Method and application.
Background technology
Cobaltosic oxide material is mainly for the production of lithium ion cell anode material lithium cobaltate.It is wide due to lithium ion battery
General application, it is also increasing to the demand of cobaltosic oxide.
In order to effectively put forward the chemical property of lithium ion battery and cycle life, often in the preparation process of cobaltosic oxide
In, adulterate the ions of some metallic elements, such as aluminium ion, magnesium ion.
The patent of invention of Application No. 200810110753.2 discloses a kind of preparation method of doped cobaltic-cobaltous oxide, should
Method is specially：By the cobalt nitrate solution containing doped chemical ion and the mixed precipitation agent solution containing ammoniacal liquor and sodium hydroxide
Mixing, it is 8.4~10.0 in pH value, temperature reacts 8~20h under the conditions of being 40~80 DEG C, and the hydrogen-oxygen containing doped chemical is made
Change cobalt precipitation；After cobalt hydroxide precipitation containing doped chemical is washed, dried, in 500~800 DEG C of temperature lower calcinations 2
~6h, obtains doped cobaltic-cobaltous oxide.
This method preparation process needs high-temperature calcination, and high-temperature calcination adds the cost of production；Meanwhile this method acquisition
Doped cobaltic-cobaltous oxide pattern is poor, purity is not high.
The patent of invention of Application No. 201210486483.1 discloses a kind of preparation side of doping spherical cobaltosic oxide
Method.This method is mainly characterized by：The mixed solution of the ion containing doped chemical is first prepared, by doping mixed solution and hydrogen-oxygen
The air for changing sodium solution and excess is passed through in reaction unit simultaneously, and stirring makes its reaction；Then filtered, washing and drying must be adulterated
Type cobaltosic oxide.
This method solve thes problems, such as that purity is low by being passed through air during the course of the reaction, but mixing of preparing of the method
Miscellaneous type cobaltosic oxide tap density is smaller, and distribution of particles is uneven；And by doped chemical and cobalt salt solution mixed preparing, mix
During closing charging, aluminium ion or magnesium ion easily form colloid with NaOH, and so as to cause the sad filter of product, yield is low.
The content of the invention
For needing high-temperature roasting in above-mentioned prior art preparation process, doped chemical easily forms glue with precipitating reagents such as NaOH
Body, and the doped cobaltic-cobaltous oxide pattern produced is poor, the problems such as distribution of particles is uneven, the embodiments of the invention provide one kind to carry
High spherical doping Co3O4The method of yield and application.
In order to reach foregoing invention purpose, the embodiment of the present invention employs following technical scheme：
One kind improves spherical doping Co3O4The method of yield, including at least following steps：
Cobalt salt solution, the enveloping agent solution for being complexed doped chemical ion, precipitant solution and air cocurrent are added anti-
Answer in device and reacted；It is 60~90 DEG C to keep reaction temperature, keeps the pH=9.0 of reaction mixture in the reaction unit
~11.0.
And correspondingly, the spherical doping Co that the embodiment of the present invention obtains3O4Application in lithium ion battery
The spherical doping Co of raising that the above embodiment of the present invention provides3O4The method of yield, by cobalt salt solution and member containing doping
The solution of plain ion is separated, and doped chemical ion is avoided into doped chemical in course of reaction together with complexing agent complexing
Ion directly contacts with precipitating reagent and directly generates the possibility of colloid；During the course of the reaction, complexing agent complexing doped chemical from
Son can slowly release ion and precipitating reagent and react during the course of the reaction, and to reach, to be effectively improved distribution of particles uneven, sad
The phenomenon of filter；In obtained doped cobaltic-cobaltous oxide cobalt content be up to 71.58% and more than, the effect through high-temperature calcination can be reached
Fruit；Final spherical doping Co3O4With yield is high, particle is small, epigranular is controllable, good sphericity, the features such as regular appearance.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, it will use below required in embodiment
Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for ability
For the those of ordinary skill of domain, on the premise of not paying creative work, it can also be obtained according to these accompanying drawings other attached
Figure.
Fig. 1 is the spherical doping Co of raising provided in an embodiment of the present invention3O4The process chart of the method for yield；
Fig. 2 is the spherical doping Co of raising provided in an embodiment of the present invention3O4Spherical doping Co prepared by the method for yield3O4
SEM figure；
Fig. 3 is the spherical doping Co of raising provided in an embodiment of the present invention3O4Spherical doping Co prepared by the method for yield3O4
XRD.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The embodiment of the present invention provides a kind of spherical doping Co of raising3O4The method of yield, including at least following steps：
Cobalt salt solution, the enveloping agent solution for being complexed doped chemical ion, precipitant solution and air cocurrent are added anti-
Answer in device and reacted；It is 60~90 DEG C to keep reaction temperature, keeps the pH=9.0 of reaction mixture in the reaction unit
~11.0.
Wherein, in any one embodiment, the concentration of cobalt salt solution is 60~150g/L.When cobalt salt concentration is less than 60g/
L, reaction time length, the guidance to actual production are little；And when cobalt salt concentration is more than 150g/L, excessive concentration, product combines too
It hurry up, the raw material for easily occurring reacting not exclusively or not participating in reaction is wrapped in inside reaction product, does not reach this hair equally
Bright purpose.
Preferably, using cobalt nitrate, cobalt chloride as cobalt salt material.Using both cobalt salts, will not be introduced after reaction
Impurity influential on product property.
In any embodiment, doped chemical ion is magnesium ion or aluminium ion.It is doped with magnesium ion and is due to
The doping of magnesium ion is influenceed less on the reversible embedding capacity of lithium, while lithium ion battery can be made to show good cyclicity
Energy.For example, the Mg of doping2+LiCoO can be occupied2Co position in lattice, so as to generate Co according to balance mechanism4+Ion, i.e.,
Hole, therefore semiconductor LiCoO2Electrical conductivity in Mg2+It can be greatly improved after doping；It is exactly that the doping of magnesium ion both carried to change one
High electrical conductivity, the complete structure of lattice is maintained again.Being doped using aluminium ion also has the poison of many advantages, first aluminium
Property is low, and cheap, density is small, Al3+Doping can improve voltage, after doping can with the structure of stable cell positive electrode,
Capacity is improved, changes cycle performance.
In any one embodiment, the mol ratio of complexing agent and the doped chemical ion is (0.5~2.0):1.
In any embodiment, concentration of the complexing agent in enveloping agent solution is 0.0275~2.06g/L, the network of the content
Mixture, when forming cobaltosic oxide, particle diameter can be effectively adjusted, avoid generating the cobaltosic oxide of bulky grain.
In a preferred embodiment, the solubility of complexing agent EDTA, EDTA in water in itself is smaller, if it is but heavy
After the agent of shallow lake, meltage can increase, and then adjust the particle diameter of the cobaltosic oxide of generation.
In a preferred embodiment, the mass concentration of precipitating reagent is 30%~35% in precipitant solution.Precipitant concentration
Less than 30%, it is impossible to reach effective hybrid reaction, and higher than 35%, the raw material that product occurs and does not react also can be quickly
Precipitate, it is unfavorable in the present invention.
, can when sodium hydroxide in mass concentration is 30%~35% as it is further preferred that precipitating reagent is sodium hydroxide
With the addition speed by combining precipitant solution, the pH of reaction mixture effectively in adjustment reaction unit.In whole reaction,
Highly important effect is played in realizations of the pH of reaction mixture to the technology of the present invention effect, and therefore, sodium hydroxide, which also has, to be adjusted
Save the effect of extent of reaction.It is molten so as to reach control cobalt salt-enveloping agent solution, precipitating reagent mainly by adjusting pH in the present invention
The addition speed of liquid and air, therefore, in order to efficiently control pH, pH real-time monitor devices can be installed in reaction unit.
In a preferred embodiment, the air mass flow is 15-30m3/ h, simultaneously, it should be ensured that reaction thoroughly terminates again
Stopping is passed through air.In the presence of the air velocity, liquid phase reactor is realized, without by high-temperature roasting, reducing life
The cost of production.
In a preferred embodiment, the reaction time entirely reacted is 8~25h.In the time interval, it is ensured that each
Individual raw material fully reacts.
In one embodiment, reaction unit is reactor, to avoid product from forming bulky grain, opens agitating device, if
It is 40~50Hz to determine stirring frequency, by stirring, the reaction mixture at each position in reaction unit can be made uniform, avoid giving birth to
Into the cobaltosic oxide of bulky grain, moreover it is possible to be that reaction mixture inner air concentration is substantially suitable so that reaction is thorough.
In the embodiment of the present invention, after the completion of reaction, in addition to the step of centrifugation or filtration washing, drying process.
Further, after drying process, in addition to broken, screening process, to obtain preferably spherical doping Co3O4。
It is provided in an embodiment of the present invention to improve spherical doping Co3O4The method of yield, by cobalt salt solution, doped chemical solution
Separately formulated, doped chemical ion forms precipitation with precipitating reagent such as NaOH during efficiently solving direct mix, and makes
Into doping type cobaltosic oxide distribution of particles it is uneven, pattern is poor, tap density is small the shortcomings that；Doped chemical is molten with cobalt salt
Liquid is separately formulated, and the doped chemical ion of complexing agent complexing can slowly release ion and be reacted with precipitating reagent during the course of the reaction,
To reach the phenomenon for being effectively improved uneven, the sad filter of distribution of particles, whole course of reaction is stable, and product easily filters, yield
It is high；Mg is done instead of ammoniacal liquor using EDTA2+、Al3+Complexing agent, avoid sharp aroma caused by ammoniacal liquor, workshop can be effectively improved
Production environment；High-temperature calcination is not needed in whole production preparation process, energy consumption is saved, reduces production cost；And this method
Obtained doping type cobaltosic oxide purity is higher, in obtained doped cobaltic-cobaltous oxide cobalt content be up to 71.58% and more than,
The effect through high-temperature calcination can be reached, the electric conductivity of battery can be effectively improved；Incorporation magnesium, aluminium can improve the electrochemistry of battery
Performance, security, cycle performance；At the same time, this is simple for process, continous way can be used to produce, and production efficiency is high, and
The stability of product batches quality is can guarantee that, is adapted to large-scale industrial production.
Further, it is provided in an embodiment of the present invention to improve spherical doping Co3O4The spherical doping of the method synthesis of yield
Co3O4Material, it can be applied in field of lithium ion battery.
In order to preferably embody the spherical doping Co of raising provided in an embodiment of the present invention3O4The method of yield, below by more
Individual embodiment further illustrates.
Embodiment 1
(1) Co in cobalt chloride solution is prepared2+Concentration be 60g/L；By MgCl2Added with EDTA molten with being made into tubbing
Liquid, control EDTA and Mg in solution2+Mol ratio be 0.5:1, it is ensured that the concentration of magnesium ion is 0.147g/ in Mg-EDTA solution
L；
(2) to reactor by above-mentioned Mg2+- EDTA complex compounds, CoCl2, precipitating reagent NaOH and air cocurrent add reactor
In, control Mg2+- EDTA complex compounds, CoCl2Flow be 150L/h, cobalt ions and Mg wherein in cobalt chloride2+- EDTA networks
Magnesium ion mol ratio in compound is 1000:6；Air mass flow is 15m3/h；Pass through the pH of precipitating reagent NaOH regulation systems, control
PH is 9.0；System temperature maintains 50 DEG C, and reaction 8h must mix the cobalt oxide wet feed of Mg ions；
(3) by after the above-mentioned cobalt oxide wet feed filtering for mixing Mg ions, washing, it is transferred in baking oven, is dried at 70 DEG C
10h；
(4) the cobalt oxide material for mixing Mg ions of above-mentioned drying crushed, sieve spherical four oxidation three that must mix Mg ions
Cobalt material, after tested, tap density 2.68g/cm3。
And the spherical cobaltic-cobaltous oxide material for mixing Mg ions that the present embodiment 1 is prepared is scanned Electronic Speculum, XRD point
Analysis, scanning electron microscope (SEM) photograph is as shown in Figure of description 2, and the XRD spectra of gained sample is as shown in Figure of description 3.
As can be seen from Figure 2, the spherical cobaltic-cobaltous oxide material for mixing Mg ions that prepared by embodiment 1, sphericity is good, and grain
Footpath is evenly distributed.
Embodiment 2
(1) Co in cobalt chloride solution is prepared2+Concentration be 80g/L；By AlCl3Added with EDTA molten with being made into tubbing
Liquid, control EDTA and Al in solution3+Mol ratio be 1:1, it is ensured that the concentration of magnesium ion is 0.22g/L in Al-EDTA solution；
(2) to reactor by above-mentioned Al3+- EDTA complex compounds, CoCl2, precipitating reagent NaOH and air cocurrent add reactor
In, control Al3+- EDTA complex compounds, CoCl2Flow be 150L/h, cobalt ions and Al wherein in cobalt chloride3+- EDTA networks
Aluminium ion mol ratio in compound is 1000:6；Air mass flow is 20m3/h；Pass through the pH of precipitating reagent NaOH regulation systems, control
PH is 9.5；System temperature maintains 65 DEG C, and reaction 10h must mix the cobaltosic oxide wet feed of Al ions；
(3) by after the above-mentioned cobaltosic oxide wet feed filtering for mixing Al ions, washing, it is transferred in baking oven, is done at 80 DEG C
Dry 9h；
(4) the cobaltosic oxide material for mixing Al ions of above-mentioned drying crushed, sieve spherical four oxygen that must mix Al ions
Change three cobalt materials, after tested, tap density 2.74g/cm3。
Embodiment 3
(1) Co in cobalt chloride solution is prepared2+Concentration be 100g/L；By MgCl2Added with EDTA molten with being made into tubbing
Liquid, control EDTA and Mg in solution2+Mol ratio be 1:2, it is ensured that the concentration of magnesium ion is 0.245g/L in Mg-EDTA solution；
(2) to reactor by above-mentioned Mg2+- EDTA complex compounds, CoCl2, precipitating reagent NaOH and air cocurrent add reactor
In, control Mg2+- EDTA complex compounds, CoCl2Flow be 200L/h, cobalt ions and Mg wherein in cobalt chloride2+- EDTA networks
Magnesium ion mol ratio in compound is 1000:6；Air mass flow is 20m3/h；Pass through the pH of precipitating reagent NaOH regulation systems, control
PH is 10.0；System temperature maintains 75 DEG C, and reaction 18h must mix the cobaltosic oxide wet feed of Mg ions；
(3) by after the above-mentioned cobaltosic oxide wet feed filtering for mixing Mg ions, washing, it is transferred in baking oven, is done at 90 DEG C
Dry 12h；
(4) the cobaltosic oxide material for mixing Mg ions of above-mentioned drying crushed, sieve spherical four oxygen that must mix Mg ions
Change three cobalt materials, after tested, tap density 2.79g/cm3。
Embodiment 4
(1) Co in cobalt chloride solution is prepared2+Concentration be 120g/L；By MgCl2Added with EDTA molten with being made into tubbing
Liquid, control EDTA and Mg in solution2+Mol ratio be 1:1.5, it is ensured that the concentration of magnesium ion is 0.294g/ in Mg-EDTA solution
L；
(2) to reactor by above-mentioned Mg2+- EDTA complex compounds, CoCl2, precipitating reagent NaOH and air cocurrent add reactor
In, control Mg2+- EDTA complex compounds, CoCl2Flow be 220L/h, cobalt ions and Mg wherein in cobalt chloride2+- EDTA networks
Magnesium ion mol ratio in compound is 1000:6；Air mass flow is 30m3/h；Pass through the pH of precipitating reagent NaOH regulation systems, control
PH is 10.5；System temperature maintains 85 DEG C, and reaction 20h must mix the cobaltosic oxide wet feed of Mg ions；
(3) by after the above-mentioned cobaltosic oxide wet feed filtering for mixing Mg ions, washing, it is transferred in baking oven, is done at 100 DEG C
Dry 7h；
(4) the cobaltosic oxide material for mixing Mg ions of above-mentioned drying crushed, sieve spherical four oxygen that must mix Mg ions
Change three cobalt materials, after tested, tap density 2.85g/cm3。
Embodiment 5
(1) Co in cobalt chloride solution is prepared2+Concentration be 150g/L；By MgCl2Added with EDTA molten with being made into tubbing
Liquid, control EDTA and Mg in solution2+Mol ratio be 1:1.5, it is ensured that the concentration of magnesium ion is 0.368g/ in Mg-EDTA solution
L；
(2) to reactor by above-mentioned Mg2+- EDTA complex compounds, CoCl2, precipitating reagent NaOH and air cocurrent add reactor
In, control Mg2+- EDTA complex compounds, CoCl2Flow be 250L/h, cobalt ions and Mg wherein in cobalt chloride2+- EDTA networks
Magnesium ion mol ratio in compound is 1000:6；Air mass flow is 20m3/h；Pass through the pH of precipitating reagent NaOH regulation systems, control
PH is 11.0；System temperature maintains 120 DEG C, and reaction 10h must mix the cobaltosic oxide wet feed of Mg ions；
(3) by after the above-mentioned cobaltosic oxide wet feed filtering for mixing Mg ions, washing, it is transferred in baking oven, is done at 120 DEG C
Dry 10h；
(4) the cobaltosic oxide material for mixing Mg ions of above-mentioned drying crushed, sieve spherical four oxygen that must mix Mg ions
Change three cobalt materials, after tested, tap density 2.89g/cm3。
Embodiment 6
(1) Co in cobalt chloride solution is prepared2+Concentration be 120g/L；By AlCl3Added with EDTA molten with being made into tubbing
Liquid, control EDTA and Al in solution3+Mol ratio be 1:1.2, it is ensured that the concentration of magnesium ion is 0.33g/L in Al-EDTA solution；
(2) to reactor by above-mentioned Al3+- EDTA complex compounds, CoCl2, precipitating reagent NaOH and air cocurrent add reactor
In, control Al3+- EDTA complex compounds, CoCl2Flow be 230L/h, cobalt ions and Al wherein in cobalt chloride3+- EDTA networks
Aluminium ion mol ratio in compound is 1000:6；Air mass flow is 25m3/h；Pass through the pH of precipitating reagent NaOH regulation systems, control
PH is 10.5；System temperature maintains 95 DEG C, and reaction 20h must mix the cobaltosic oxide wet feed of Al ions；
(3) by after the above-mentioned cobaltosic oxide wet feed filtering for mixing Al ions, washing, it is transferred in baking oven, is done at 100 DEG C
Dry 8h；
(4) the cobaltosic oxide material for mixing Al ions of above-mentioned drying crushed, sieve spherical four oxygen that must mix Al ions
Change three cobalt materials, after tested, tap density 2.95g/cm3。
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modification, equivalent substitution or improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. one kind improves spherical doping Co3O4The method of yield, including at least following steps：
Cobalt salt solution, the enveloping agent solution for being complexed doped chemical ion, precipitant solution and air cocurrent are added into reaction dress
Reacted in putting；It is 60~90 DEG C to keep reaction temperature, keep the pH=9.0 of reaction mixture in the reaction unit~
11.0。
2. spherical doping Co is improved as claimed in claim 13O4The method of yield, it is characterised in that：The cobalt salt solution it is dense
Spend for 60~150g/L；And/or the cobalt salt is cobalt nitrate, cobalt chloride.
3. spherical doping Co is improved as claimed in claim 13O4The method of yield, it is characterised in that：The enveloping agent solution
In, the mol ratio of the complexing agent and the doped chemical ion is (0.5~2.0):1；And/or the doped chemical is aluminium member
Element or magnesium elements.
4. spherical doping Co is improved as claimed in claim 13O4The method of yield, it is characterised in that：In the enveloping agent solution
The concentration of complexing agent is 0.0275~2.06g/L.
5. spherical doping Co is improved as claimed in claim 13O4The method of yield, it is characterised in that：The air mass flow is
15-30m3/h。
6. spherical doping Co is improved as claimed in claim 13O4The method of yield, it is characterised in that：The precipitating reagent is hydrogen-oxygen
Change sodium；And/or the mass concentration of the sodium hydroxide is 30%~35%.
7. spherical doping Co is improved as claimed in claim 13O4The method of yield, it is characterised in that：The complexing agent is
EDTA。
8. spherical doping Co is improved as claimed in claim 13O4The method of yield, it is characterised in that：Also need to the reaction mixing
Liquid is stirred by 40~50Hz stirring frequency；And/or 8~25h of reaction time of the reaction.
9. spherical doping Co is improved as claimed in claim 13O4The method of yield, it is characterised in that：The air is passed through reaction
The bottom of mixed liquor.
10. the spherical doping Co of raising as described in claim 1-2 is any3O4The spherical doping Co of the method production of yield3O4
Application in lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710499182.5A CN107342408A (en) | 2017-06-27 | 2017-06-27 | Improve spherical doping Co3O4The method of yield and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710499182.5A CN107342408A (en) | 2017-06-27 | 2017-06-27 | Improve spherical doping Co3O4The method of yield and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107342408A true CN107342408A (en) | 2017-11-10 |
Family
ID=60221198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710499182.5A Pending CN107342408A (en) | 2017-06-27 | 2017-06-27 | Improve spherical doping Co3O4The method of yield and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107342408A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108373175A (en) * | 2018-01-23 | 2018-08-07 | 湖南雅城新材料有限公司 | Aluminium doped cobaltic-cobaltous oxide and its preparation method and application |
| CN108807881A (en) * | 2018-05-21 | 2018-11-13 | 兰州金川新材料科技股份有限公司 | A kind of body mutually mixes the preparation method of aluminium cobaltosic oxide |
| CN109354075A (en) * | 2018-09-30 | 2019-02-19 | 衢州华友钴新材料有限公司 | A kind of small particle uniformly mixes the preparation method of aluminium spherical cobaltic-cobaltous oxide |
| CN109896552A (en) * | 2019-02-19 | 2019-06-18 | 湖南中伟新能源科技有限公司 | A kind of preparation method for mixing aluminium lithium ion anode material presoma |
| CN112537802A (en) * | 2020-12-08 | 2021-03-23 | 衢州华友钴新材料有限公司 | Preparation method of high-voltage lithium battery precursor doped with cobalt hydroxide |
| CN113697865A (en) * | 2021-08-27 | 2021-11-26 | 湖南中伟新能源科技有限公司 | Cobaltosic oxide, preparation method thereof and lithium ion battery |
| CN114349066A (en) * | 2021-12-28 | 2022-04-15 | 荆门市格林美新材料有限公司 | Preparation method of magnesium-aluminum co-doped lithium cobaltate precursor |
| CN115028208A (en) * | 2022-07-22 | 2022-09-09 | 衢州华友钴新材料有限公司 | Cobaltosic oxide material, preparation method, positive electrode and lithium battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172118A (en) * | 2013-03-19 | 2013-06-26 | 南通瑞翔新材料有限公司 | Method for preparing spherical cobaltosic oxide and manganese oxide |
| CN103359794A (en) * | 2012-03-30 | 2013-10-23 | 北京当升材料科技股份有限公司 | Spherical cobaltosic oxide and preparation method thereof |
| CN103715418A (en) * | 2012-09-28 | 2014-04-09 | 北京当升材料科技股份有限公司 | Preparation method for spherical cobaltosic oxide |
| CN103833088A (en) * | 2012-11-23 | 2014-06-04 | 宁波科博特钴镍有限公司 | Method for preparing doped spherical cobaltosic oxide |
| CN104986807A (en) * | 2015-04-23 | 2015-10-21 | 金川集团股份有限公司 | Spherical tricobalt tetraoxide preparation method |
| CN105098171A (en) * | 2015-07-03 | 2015-11-25 | 浙江亿利泰钴镍材料有限公司 | Preparation method of cobalt-aluminum oxide for lithium-ion power battery |
| CN106340643A (en) * | 2015-07-10 | 2017-01-18 | 北京当升材料科技股份有限公司 | Method for preparing large-grain spherical cobaltosic oxide |
| CN106587170A (en) * | 2016-11-30 | 2017-04-26 | 兰州金川新材料科技股份有限公司 | Preparation method of cobaltosic oxide with rare earth element doped body phase |
-
2017
- 2017-06-27 CN CN201710499182.5A patent/CN107342408A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103359794A (en) * | 2012-03-30 | 2013-10-23 | 北京当升材料科技股份有限公司 | Spherical cobaltosic oxide and preparation method thereof |
| CN103715418A (en) * | 2012-09-28 | 2014-04-09 | 北京当升材料科技股份有限公司 | Preparation method for spherical cobaltosic oxide |
| CN103833088A (en) * | 2012-11-23 | 2014-06-04 | 宁波科博特钴镍有限公司 | Method for preparing doped spherical cobaltosic oxide |
| CN103172118A (en) * | 2013-03-19 | 2013-06-26 | 南通瑞翔新材料有限公司 | Method for preparing spherical cobaltosic oxide and manganese oxide |
| CN104986807A (en) * | 2015-04-23 | 2015-10-21 | 金川集团股份有限公司 | Spherical tricobalt tetraoxide preparation method |
| CN105098171A (en) * | 2015-07-03 | 2015-11-25 | 浙江亿利泰钴镍材料有限公司 | Preparation method of cobalt-aluminum oxide for lithium-ion power battery |
| CN106340643A (en) * | 2015-07-10 | 2017-01-18 | 北京当升材料科技股份有限公司 | Method for preparing large-grain spherical cobaltosic oxide |
| CN106587170A (en) * | 2016-11-30 | 2017-04-26 | 兰州金川新材料科技股份有限公司 | Preparation method of cobaltosic oxide with rare earth element doped body phase |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108373175A (en) * | 2018-01-23 | 2018-08-07 | 湖南雅城新材料有限公司 | Aluminium doped cobaltic-cobaltous oxide and its preparation method and application |
| CN108373175B (en) * | 2018-01-23 | 2020-08-21 | 湖南雅城新材料有限公司 | Aluminum-doped cobaltosic oxide and preparation method and application thereof |
| CN108807881A (en) * | 2018-05-21 | 2018-11-13 | 兰州金川新材料科技股份有限公司 | A kind of body mutually mixes the preparation method of aluminium cobaltosic oxide |
| CN109354075A (en) * | 2018-09-30 | 2019-02-19 | 衢州华友钴新材料有限公司 | A kind of small particle uniformly mixes the preparation method of aluminium spherical cobaltic-cobaltous oxide |
| CN109896552A (en) * | 2019-02-19 | 2019-06-18 | 湖南中伟新能源科技有限公司 | A kind of preparation method for mixing aluminium lithium ion anode material presoma |
| CN112537802A (en) * | 2020-12-08 | 2021-03-23 | 衢州华友钴新材料有限公司 | Preparation method of high-voltage lithium battery precursor doped with cobalt hydroxide |
| CN112537802B (en) * | 2020-12-08 | 2022-11-22 | 衢州华友钴新材料有限公司 | Preparation method of high-voltage lithium battery precursor doped with cobalt hydroxide |
| CN113697865A (en) * | 2021-08-27 | 2021-11-26 | 湖南中伟新能源科技有限公司 | Cobaltosic oxide, preparation method thereof and lithium ion battery |
| CN114349066A (en) * | 2021-12-28 | 2022-04-15 | 荆门市格林美新材料有限公司 | Preparation method of magnesium-aluminum co-doped lithium cobaltate precursor |
| CN114349066B (en) * | 2021-12-28 | 2023-11-24 | 荆门市格林美新材料有限公司 | Preparation method of magnesium-aluminum co-doped lithium cobaltate precursor |
| CN115028208A (en) * | 2022-07-22 | 2022-09-09 | 衢州华友钴新材料有限公司 | Cobaltosic oxide material, preparation method, positive electrode and lithium battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107342408A (en) | Improve spherical doping Co3O4The method of yield and application | |
| Yang et al. | Preparation of porous ZnO/ZnFe2O4 composite from metal organic frameworks and its applications for lithium ion batteries | |
| CN104979546B (en) | Preparation method of single-crystal-morphology lithium ion battery ternary cathode material | |
| Ni et al. | Molten salt synthesis and electrochemical properties of spherical LiFePO4 particles | |
| CN105304893A (en) | Preparation method of lithium ion battery anode active material lithium nickel manganese oxide | |
| Xiao et al. | Effects of structural patterns and degree of crystallinity on the performance of nanostructured ZnO as anode material for lithium-ion batteries | |
| CN112349899B (en) | Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN105322154B (en) | Electrode active substance precursor nickel manganese oxide with special morphology | |
| CN103708434B (en) | LiFePO 4 material and preparation method thereof | |
| Chen et al. | Chemical reaction controlled synthesis of Cu 2 O hollow octahedra and core–shell structures | |
| Li et al. | Lead citrate precursor route to synthesize nanostructural lead oxide from spent lead acid battery paste | |
| CN105060351B (en) | Flower-like cobaltosic oxide material composed of nanoparticles and preparation method thereof | |
| Ramasami et al. | Synthesis, exploration of energy storage and electrochemical sensing properties of hematite nanoparticles | |
| Zhang et al. | 3D hierarchical flower of copper molybdate Cu3Mo2O9: Synthesis, nanostructure and lithium storage properties | |
| CN103560246A (en) | Preparation method of positive material lithium iron phosphate of lithium ion battery | |
| CA2878918A1 (en) | Method for preparing lithium metal phosphor oxide | |
| JP6182673B2 (en) | Method for producing lithium iron phosphate | |
| Neale et al. | Effect of synthesis pH and EDTA on iron hexacyanoferrate for sodium-ion batteries | |
| CN110504447A (en) | A kind of nickel cobalt manganese presoma of Fluorin doped and the preparation method and application thereof | |
| CN106745337A (en) | A kind of LiNi1/3Co1/3Mn1/3O2Preparation method | |
| CN104091950A (en) | Method for preparing lithium iron phosphate material with hydrothermal process | |
| Yalçın et al. | Synthesis of Sn-doped Li-rich NMC as a cathode material for Li-ion batteries | |
| Zhu et al. | Nanostructured titanium phosphates prepared via hydrothermal reaction and their electrochemical Li-and Na-ion intercalation properties | |
| Liu et al. | Improving the electrochemical performance of single crystal LiNi0. 5Mn1. 5O4 cathode materials by Y–Ti doping and unannealing process | |
| Malik et al. | Effect of Synthesis Method on the Electrochemical Performance of LiNi x MnCo 1-xy O 2 (NMC) Cathode for Li-Ion Batteries: A Review |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171110 |