CN109509875A - A kind of high-rate type monocrystalline nickel-cobalt lithium manganate cathode material and preparation method thereof - Google Patents
A kind of high-rate type monocrystalline nickel-cobalt lithium manganate cathode material and preparation method thereof Download PDFInfo
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- 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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- 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 discloses a kind of high-rate type monocrystalline nickel-cobalt lithium manganate cathode materials and preparation method thereof, including the monocrystalline internal layer being made of ternary nickel, cobalt and manganese oxide and the package outer layer being made of bimetallic lithium salts, the chemical general formula of the high-rate type monocrystalline nickel-cobalt lithium manganate cathode material are as follows: LixNiaCobMncYdMo3dO2, wherein 1≤x≤l.10,0 < a < l, 0 <b < 1,0 < c < 1,0 < d≤0.12 and a+b+c+4d=1.The present invention has wrapped up one layer of bimetallic lithium salts after prepared by monocrystalline type nickel-cobalt-manganternary ternary anode material, and wrapping layer can effectively inhibit the side reaction between material and electrolyte, greatly improves the high rate performance and cycle performance of material.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of high-rate type monocrystalline nickle cobalt lithium manganate anode material
Material and preparation method.
Background technique
Ternary material was most proposed to can be used as the positive electrode of lithium ion battery early in 1999, be replaced using Co, Mn
LiNiO2In Ni prepare a series of LiNi1-x-yCoxMnyO2Solid-solution material, and find the physics of the solid-solution material system
Performance and chemical property change with the change of transition metal element ratio, and changing rule can summarize are as follows: nickel element is
Main capacity source, nickel content increase can greatly improve the specific capacity of material, and with another capacity source cobalt phase ratio, electricity
It is more matched between pressure area with existing electrolyte system；But crossing high nickel content will lead to cationic mixing phenomenon aggravation, deteriorate material
Cycle performance, high rate performance and the security performance of material, coulombic efficiency can also gradually decrease, and cobalt element can also provide capacity, fit
When content cobalt effectively stable laminated structure and can inhibit cationic mixing, the electron conduction of material is improved, material multiplying power is improved
Performance；But the voltage range that cobalt element plays capacity is higher than current conventional 4.2V blanking voltage, and the cobalt of too high amount will increase
Cost.Inertia and stable Mn4+ reinforcing material structural stability, significantly improve cycle performance and thermal stability, but manganese element
Capacity is not provided, the gram volume and energy density of material can be significantly reduced.
Tertiary cathode material is all largely the secondary spherical particle that small grains are agglomerated at present, and secondary spherical particle
Primary particle between there are gap, you can't get packages on part primary particle surface when the package processing of surface, this will be difficult to keep away
Result in second particle whole package with exempting from is uneven, the result is that lead to the electrical property for influencing battery, especially battery is followed
Ring performance.In addition Li [Ni, Co, Mn] O2High rate performance be not it is highly desirable, hinder it in mixed type electrical source of power
Using this is mainly related with the electronic conductivity of material.In addition for the material under high charge-discharge voltage, cyclical stability is poor.
Summary of the invention
To cope with prior art Li [Ni, Co, Mn] O2The shortcomings that high rate performance is undesirable, cyclical stability is poor, this
Invention provides a kind of high-rate type monocrystalline nickel-cobalt lithium manganate cathode material, and its technical solution is as follows:
The high-rate type monocrystalline nickel-cobalt lithium manganate cathode material includes in the monocrystalline being made of ternary nickel, cobalt and manganese oxide
Layer and the package outer layer being made of bimetallic lithium salts, the chemical general formula of the high-rate type monocrystalline nickel-cobalt lithium manganate cathode material
Are as follows: LixNiaCobMncYdMo3dO2, wherein 1≤x≤l.10,0 < a < l, 0 <b < 1,0 < c < 1,0 < d≤0.12 and a+b+c+4d=
1。
Further, the molar ratio of the ternary nickel, cobalt and manganese oxide and bimetallic lithium salts is 1:0.02~0.06.
Further, it is described package outer layer with a thickness of 10-200nm.
Another object of the present invention is to provide a kind of preparation sides of high-rate type monocrystalline nickel-cobalt lithium manganate cathode material
Method, comprising the following steps:
S1, ternary precursor is prepared: by the sulfate liquor of the sulfate liquor of nickel, the sulfate liquor of cobalt, manganese by change
General formula metering proportion ingredient is learned, pure water is added and is mixed, ascorbic acid stirring is added and is configured to mixed solution, will mix molten
Liquid, NaOH solution and ammonia spirit are added in reaction kettle and are mixed, and sediment is obtained after fully reacting, sediment is taken out
Filter, drying, obtain the ternary precursor of nickel cobalt manganese hydroxide；
S2, it prepares nickel-cobalt-manganese ternary material: the ternary precursor of step S1 preparation is sintered, by lithium source and burn
Ternary precursor after the completion of knot carries out mixing and ball milling, obtains mixed powder, then mixed powder is carried out high temperature sintering, can obtain
To the nickel-cobalt-manganese ternary material of mono-crystalline structures；
S3, package processing: bimetallic lithium salts is weighed according to the molar ratio with ternary nickel, cobalt and manganese oxide, and will be weighed double
Metal lithium salts and the nickel-cobalt-manganese ternary material of preparation are put into high-speed mixer and mixing, take out after the completion of mixing and carry out calcination processing, i.e.,
High-rate type monocrystalline nickel-cobalt lithium manganate cathode material can be obtained.
Preferably, in step S1, in the mixing process, pH value control is 11.0~12.0；Reaction temperature is 35
~65 DEG C, 400~500r/min of mixing speed.
Preferably, in step S1, drying preferably uses blast drier, and drying time is 8~10h.
Preferably, in step S2, the lithium source be lithium hydroxide and or lithium carbonate；In step S3, the bimetallic lithium salts
For LiYMo3O8。
Preferably, in step S2, the high-temperature sintering process is to be warming up to 550-650 DEG C first to carry out the preliminary of 2-18h
Sintering, the two-step sintering of 900~970 DEG C of progress 8-24h of heating after the completion of preliminary sintering.
Preferably, in step S3, the temperature of the calcining is 600-800 DEG C, calcination time 10-16h.
Beneficial effects of the present invention:
(1) present invention wraps up one layer of bimetallic lithium salts on the basis of monocrystalline type nickel-cobalt-manganternary ternary anode material, and package is outer
Layer can effectively inhibit the side reaction between material and electrolyte, greatly improve the cycle performance and security performance of material.
(2) contain lithium ion in package cladding material of the present invention, positive electrode and electrolyte can not only be prevented
Directly side reaction occurs for contact, while can make ionic conduction with higher between positive electrode and the reaction interface of electrolyte
Property, so that impedance is reduced, to improve the high rate performance of positive electrode；While wrapping up the molybdenum ion in outer layer during the charging process
It will be oxidized, and be improved the specific discharge capacity of positive electrode further, the package of molybdenum ion is for the forthright again of material
It can also make moderate progress.
Detailed description of the invention
Fig. 1 is the SEM figure that positive electrode is made in the embodiment of the present invention 1.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Embodiment 1
The preparation method of the monocrystalline type ternary cathode material of lithium ion battery of bimetallic lithium salts package of the present invention, packet
Include following steps:
S1, coprecipitation prepare spherical ternary precursor Ni0.5Co0.2Mn0.3(OH)2: LITHIUM BATTERY is taken by 5:2:3 molar ratio
NiSO4、CoSO4And MnSO4High purity water is added after mixing, the solution 6L of 1.0mol/L is made, ascorbic acid 48g is added, is mixed
Close solution；By the way of peristaltic pump cocurrent, the NaOH solution of mixed solution, the ammonia spirit of 1mol/L, 2mol/L are placed in
It is mixed and reacts in reaction kettle, control pH value is 11.5, and reaction temperature is 50 DEG C, mixing speed 400r/min, will
It reacts the precipitating generated to filter 5 times by blower, then dries 8h with blast drier, obtain nickel cobalt manganese hydroxide, i.e., three
First presoma；
The preparation of S2, nickel-cobalt-manganese ternary material: the hydrogen-oxygen of the ternary precursor, 1.10mol LITHIUM BATTERY that take 1mol to prepare
Change lithium and be placed in ball milling in ball grinder, obtains mixed powder；Mixed powder is placed in alumina crucible, is then burnt at 550 DEG C
6h is tied, continues to increase temperature to 15h is sintered at 970 DEG C, obtains monocrystalline type nickel-cobalt-manganese ternary material；
S3, the processing of nickel-cobalt-manganese ternary material bimetallic lithium salts package: 1 is pressed with nickel-cobalt-manganese ternary material and bimetallic lithium salts:
0.02 molar ratio weighs bimetallic lithium salts, and bimetallic lithium salts and nickel-cobalt-manganese ternary material are put into take out after high mixer 1h and forged
It burns；Calcination temperature is 700 DEG C, calcination time 4h, can obtain high-rate type monocrystalline nickel-cobalt lithium manganate cathode material.
Embodiment 2
The preparation method of the monocrystalline type ternary cathode material of lithium ion battery of bimetallic lithium salts package, includes the following steps:
S1, coprecipitation prepare spherical ternary precursor Ni0.5Co0.2Mn0.3(OH)2: LITHIUM BATTERY is taken by 5:2:3 molar ratio
NiSO4、CoSO4And MnSO4High purity water is added after mixing, the solution 6L of 1.0mol/L is made, ascorbic acid 48g is added, is mixed
Close solution；By the way of peristaltic pump cocurrent, the NaOH solution of mixed solution, the ammonia spirit of 1mol/L, 2mol/L are placed in
It is mixed and reacts in reaction kettle, control pH value is 11.50, and reaction temperature is 50 DEG C, mixing speed 500r/min, will
It reacts the precipitating generated to filter 5 times by blower, then dries 10h with blast drier, obtain nickel cobalt manganese hydroxide, i.e., three
First presoma；
The preparation of S2, nickel-cobalt-manganese ternary material: the hydrogen-oxygen of the ternary precursor, 1.08mol LITHIUM BATTERY that take 1mol to prepare
Change lithium and be placed in ball milling in ball grinder, obtains mixed powder；Mixed powder is placed in alumina crucible, is then burnt at 600 DEG C
6h is tied, continues to increase temperature to 15h is sintered at 950 DEG C, obtains monocrystalline type nickel-cobalt-manganese ternary material；
S3, the processing of nickel-cobalt-manganese ternary material bimetallic lithium salts package: 1 is pressed with nickel-cobalt-manganese ternary material and bimetallic lithium salts:
0.04 molar ratio weighs bimetallic lithium salts, takes out after bimetallic lithium salts and nickel-cobalt-manganese ternary material are put into high mixer 0.5h
Calcining calcines at 800 DEG C, calcination time 2h, can obtain high-rate type monocrystalline nickel-cobalt lithium manganate cathode material.
Embodiment 3
The preparation method of the monocrystalline type ternary cathode material of lithium ion battery of bimetallic lithium salts package, includes the following steps:
S1, coprecipitation prepare spherical ternary precursor Ni0.5Co0.2Mn0.3(OH)2: LITHIUM BATTERY is taken by 5:2:3 molar ratio
NiSO4、CoSO4And MnSO4High purity water is added after mixing, the solution 6L of 1.0mol/L is made, ascorbic acid 48g is added, is mixed
Close solution；By the way of peristaltic pump cocurrent, the NaOH solution of mixed solution, the ammonia spirit of 1mol/L, 2mol/L are placed in
It is mixed and reacts in reaction kettle, control pH value is 11.50, and reaction temperature is 50 DEG C, mixing speed 500r/min, will
It reacts the precipitating generated to filter 5 times by blower, then dries 10h with blast drier, obtain nickel cobalt manganese hydroxide, i.e., three
First presoma；
The preparation of S2, nickel-cobalt-manganese ternary material: the hydrogen-oxygen of the ternary precursor, 1.10mol LITHIUM BATTERY that take 1mol to prepare
Change lithium and be placed in ball milling in ball grinder, obtains mixed powder；Mixed powder is placed in alumina crucible, is then burnt at 700 DEG C
3h is tied, continues to increase temperature to 8h is sintered at 900 DEG C, obtains monocrystalline type nickel-cobalt-manganese ternary material；
S3, the processing of nickel-cobalt-manganese ternary material bimetallic lithium salts package: 1 is pressed with nickel-cobalt-manganese ternary material and bimetallic lithium salts:
0.06 molar ratio weighs bimetallic lithium salts, and bimetallic lithium salts and nickel-cobalt-manganese ternary material are put into take out after high mixer 2h and forged
It burns, calcination temperature can obtain high-rate type monocrystalline nickel-cobalt lithium manganate cathode material at 600 DEG C, calcination time 10h.
Comparative example 1
A kind of anode material for lithium-ion batteries, the preparation method of the anode material for lithium-ion batteries, includes the following steps:
S1, coprecipitation prepare spherical ternary precursor Ni0.5Co0.2Mn0.3(OH)2: LITHIUM BATTERY is taken by 5:2:3 molar ratio
NiSO4、CoSO4And MnSO4High purity water is added after mixing, the solution 6L of 1.0mol/L is made, ascorbic acid 48g is added, is mixed
Close solution；By the way of peristaltic pump cocurrent, the NaOH solution of mixed solution, the ammonia spirit of 1mol/L, 2mol/L are placed in
It is mixed and reacts in reaction kettle, control pH value is 11.4, and reaction temperature is 50 DEG C, mixing speed 500r/min, will
The precipitating generated is reacted by blower suction filtration 5 times or more, is then dried 10h with blast drier, is obtained nickel cobalt manganese hydroxide,
That is ternary precursor；
The preparation of S2, nickel-cobalt-manganese ternary material: by the above-mentioned ternary precursor prepared of 1mol, the lithium hydroxide of LITHIUM BATTERY
It is placed in ball milling in ball grinder, obtains mixed powder, wherein the molar ratio of ternary precursor and LITHIUM BATTERY lithium hydroxide is 1:1.10；
Mixed powder is placed in alumina crucible, is then sintered 6h at 600 DEG C, continues to increase temperature to being sintered 15h at 950 DEG C,
Obtain monocrystalline type nickel-cobalt-manganese ternary material, i.e. anode material for lithium-ion batteries.
Comparative example 2:
A kind of preparation method of ternary cathode material of lithium ion battery includes the following steps: that S1, coprecipitation preparation are spherical
Ternary precursor Ni0.5Co0.2Mn0.3(OH)2: LITHIUM BATTERY NiSO is taken by 5:2:3 molar ratio4、CoSO4And MnSO4It is added after mixing
The solution 6L of 1.0mol/L is made in high purity water, and ascorbic acid 48g is added, obtains mixed solution；Using the side of peristaltic pump cocurrent
Formula, by mixed solution, the ammonia spirit of 1mol/L, 2mol/L NaOH solution be placed in reaction kettle be mixed react,
Controlling pH value is 11.6, and reaction temperature is 50 DEG C, mixing speed 500r/min, and the precipitating that reaction is generated is filtered by blower
5 times or more, 10h then is dried with blast drier, obtains nickel cobalt manganese hydroxide, i.e. ternary precursor；
The preparation of S2, nickel-cobalt-manganese ternary material: the hydrogen-oxygen of the ternary precursor, 1.10mol LITHIUM BATTERY that take 1mol to prepare
Change lithium and be placed in ball milling in ball grinder, obtains mixed powder；Mixed powder is placed in alumina crucible, is then burnt at 500 DEG C
9h is tied, continues to increase temperature to 15h is sintered at 930 DEG C, obtains nickel-cobalt-manganese ternary material；
S3, the processing of nickel-cobalt-manganese ternary material bimetallic lithium salts package: 1 is pressed with nickel-cobalt-manganese ternary material and bimetallic lithium salts:
0.08 molar ratio weighs bimetallic lithium salts, takes out after bimetallic lithium salts and nickel-cobalt-manganese ternary material are put into high mixer 1.5h
Calcining, calcination temperature can obtain high-rate type monocrystalline nickel-cobalt lithium manganate cathode material in 650 (550) DEG C, calcination time 4h.
Battery charging and discharging specific capacity test: the lithium ion cell positive material for respectively obtaining embodiment 1-3, comparative example 1-2
Positive plate is made in material, then assembles them into " 2032 " type button cell with routine techniques, in 2.75-4.3V voltage range, no
With charge-discharge test is carried out under current density, the charging and discharging capacity of different materials is recorded, as a result referring to table 1, wherein rear 1C is followed
Ring 50 times, the discharge capacity * 100% of discharge capacity/the first week of cycle efficieny=50th week of battery.
1 embodiment 1-3's of table and comparative example 1-2 buckles electric performance test result
From table 1 it follows that the molar ratio of nickel-cobalt-manganese ternary material of the present invention and bimetallic lithium salts 1:0.06 with
When lower, battery capacity made from nickel-cobalt-manganese ternary material is obviously higher than what is do not wrapped up；When package amount is 1:0.04, battery 0.1C
Discharge capacity is up to 161.55mAh/g, and the first discharge specific capacity of battery made from the ternary material not wrapped up is only
159.72mAh/g, this is because bimetallic lithium salts wrapper material has no effect on the insertion and abjection of lithium ion, wrapping layer is deposited
The polarization of material has no influence on cyclic process for the first time；After 50 weeks circulations, battery made from the ternary material that does not wrap up
Cycle performance is worst.
From table 1 it follows that the high rate performance of material is best, 2C when the package amount of bimetallic lithium salts is 1:0.04
It is apparently higher than with 5C discharge capacity and not to wrap up；From comparative example 2 as can be seen that when package amount is 1:0.08, relative to not wrapping
The high rate performance wrapped up in is deteriorated instead, and data measured declines instead, this is because increasing the barrier of diffusive migration when wrapping layer is blocked up
Hinder, lead to the impedance increase of material after package, so that high rate performance decline is obvious.
Embodiment described above only describe the preferred embodiments of the invention, not to model of the invention
It encloses and is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical side of the invention
The various changes and improvements that case is made should all be fallen into the protection scope that claims of the present invention determines.
Claims (9)
1. a kind of high-rate type monocrystalline nickel-cobalt lithium manganate cathode material, which is characterized in that the high-rate type monocrystalline nickel cobalt mangaic acid
Lithium anode material includes the monocrystalline internal layer being made of ternary nickel, cobalt and manganese oxide and the package outer layer that is made of bimetallic lithium salts, institute
State the chemical general formula of high-rate type monocrystalline nickel-cobalt lithium manganate cathode material are as follows: LixNiaCobMncYdMo3dO2, wherein 1≤x≤
L.10,0 < a < l, 0 <b < 1,0 < c < 1,0 < d≤0.12 and a+b+c+4d=1.
2. high-rate type monocrystalline nickel-cobalt lithium manganate cathode material according to claim 1, which is characterized in that the nickel ternary
The molar ratio of cobalt and manganese oxide and bimetallic lithium salts is 1:0.02 ~ 0.06.
3. high-rate type monocrystalline nickel-cobalt lithium manganate cathode material according to claim 1, which is characterized in that outside the package
Layer with a thickness of 10-200nm.
4. a kind of preparation side of high-rate type monocrystalline nickel-cobalt lithium manganate cathode material according to claim 1 to 3
Method, it is characterised in that: the following steps are included:
S1, ternary precursor is prepared: the sulfate liquor of the sulfate liquor of nickel, the sulfate liquor of cobalt, manganese is logical by chemistry
Formula metering proportion ingredient, be added pure water mixed, add ascorbic acid stirring be configured to mixed solution, by mixed solution,
NaOH solution and ammonia spirit are added in reaction kettle and are mixed, and sediment is obtained after fully reacting, sediment is filtered and
Drying and processing obtains the ternary precursor of nickel cobalt manganese hydroxide；
S2, prepare nickel-cobalt-manganese ternary material: to step S1 preparation ternary precursor be sintered, by lithium source be sintered
Ternary precursor after carries out mixing and ball milling, obtains mixed powder, then mixed powder is carried out high temperature sintering, list can be obtained
The nickel-cobalt-manganese ternary material of crystal structure；
S3, package processing: weighing bimetallic lithium salts according to the molar ratio with ternary nickel, cobalt and manganese oxide, and by weighed bimetallic
Lithium salts and the nickel-cobalt-manganese ternary material of preparation are put into high-speed mixer and mixing, take out after the completion of mixing and carry out calcination processing, can obtain
High-rate type monocrystalline nickel-cobalt lithium manganate cathode material.
5. the preparation method of high-rate type monocrystalline nickel-cobalt lithium manganate cathode material according to claim 4, it is characterised in that:
In step S1, in the mixing process, pH value control is 11.0 ~ 12.0；Reaction temperature is 35 ~ 65 DEG C, mixing speed 400
~500r/min。
6. the preparation method of high-rate type monocrystalline nickel-cobalt lithium manganate cathode material according to claim 4, which is characterized in that
In step S1, drying and processing preferably uses blast drier, and drying time is 8 ~ 10h.
7. the preparation method of high-rate type monocrystalline nickel-cobalt lithium manganate cathode material according to claim 4, it is characterised in that:
In step S2, the lithium source be lithium hydroxide and or lithium carbonate；In step S3, the bimetallic lithium salts is LiYMo3O8。
8. the preparation method of high-rate type monocrystalline nickel-cobalt lithium manganate cathode material according to claim 4, it is characterised in that:
In step S2, the high-temperature sintering process is the preliminary sintering for being warming up to 550-650 DEG C of progress 2-18h first, has tentatively been sintered
At the two-step sintering of 900 ~ 970 DEG C of progress 8-24h of rear heating.
9. the preparation method of high-rate type monocrystalline nickel-cobalt lithium manganate cathode material according to claim 4, it is characterised in that:
In step S3, the temperature of the calcining is 600-800 DEG C, calcination time 10-16h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811417199.2A CN109509875B (en) | 2018-11-26 | 2018-11-26 | High-rate single crystal lithium nickel cobalt manganese oxide cathode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811417199.2A CN109509875B (en) | 2018-11-26 | 2018-11-26 | High-rate single crystal lithium nickel cobalt manganese oxide cathode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109509875A true CN109509875A (en) | 2019-03-22 |
| CN109509875B CN109509875B (en) | 2021-09-10 |
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| CN110867580A (en) * | 2019-11-22 | 2020-03-06 | 四川新锂想能源科技有限责任公司 | Method for preparing nickel cobalt lithium manganate single crystal positive electrode material by strontium doping |
| CN112002901A (en) * | 2020-08-12 | 2020-11-27 | 中南大学 | Metal compound coated ternary cathode material and preparation method thereof |
| CN112830524A (en) * | 2019-11-22 | 2021-05-25 | 中国科学院大连化学物理研究所 | Transition metal oxide positive electrode material of single crystal lithium and preparation method and application thereof |
| CN113036115A (en) * | 2021-02-07 | 2021-06-25 | 东莞市创明电池技术有限公司 | Graded high-nickel ternary composite material, preparation method thereof and lithium secondary battery |
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| CN113036115A (en) * | 2021-02-07 | 2021-06-25 | 东莞市创明电池技术有限公司 | Graded high-nickel ternary composite material, preparation method thereof and lithium secondary battery |
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