CN106299342B - K ion doping and high-voltage spinel/carbon double-coating lithium-rich anode material and preparation method thereof - Google Patents
K ion doping and high-voltage spinel/carbon double-coating lithium-rich anode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of K ion dopings and high-voltage spinel/carbon double-coating lithium-rich anode material and preparation method thereof.The lithium-rich anode material includes the nucleome of K modification by ion-doping and the high-voltage spinel for being coated on core surface/carbon two-coat；Nucleome are as follows: Li1.2‑xKxMn0.6‑yNi0.2‑yCo2yO2, wherein x=0.00-0.1, y=0.00-0.05；High-voltage spinel/carbon two-coat high voltage appearance spinel layer group is divided into Li1‑xKxMn1.5‑ yNi0.5‑yCo2yO4, wherein x=0.0-0.2, y=0.0-0.1；Carbon coating layer is the composite construction of dopamine condensate pyrolytic carbon and redox graphene.Preparation method includes the nucleome that K modification by ion-doping is prepared by spray drying technology, dopamine condensate is coated on its surface, the cladding of graphene oxide is carried out on this basis, by follow-up sintering, to prepare K ion doping and high-voltage spinel/carbon double-coating lithium-rich anode material.The present invention has modification procedure easily-controllable, can significantly improve lithium-rich anode material chemical property.
Description
Technical field
The present invention relates to modification of lithium ion battery anode material technical fields, more particularly to have both K ion doping and height electricity
Pointing spar/carbon double-coating lithium-rich anode material and preparation method thereof, lithium battery anode and lithium battery.
Background technique
The energy and environmental crisis have become puzzlement very important two problems of today's society, therefore to high performance energy
More stringent requirements are proposed for storage and the development of conversion equipment.Lithium ion battery has specific energy/power close as secondary cell
Degree is high, have extended cycle life, memory-less effect, pollution-free and the advantages such as have a safety feature, and has on miniaturized electronics
Very extensive application.The new market demand requires next generation LIB(lithium ion battery) technology other than having traditional advantage,
Also there are higher energy/power density, better cyclical stability and lower production and operation cost.Wherein high-performance,
The exploitation of inexpensive positive electrode is the key that LIB is used practically in the fields such as electric car and large-scale stationary electric power plant.
In recent years, rich lithium material, xLi [Li1/3Mn2/3]O2•(1-x)LiMO2Wherein M=MnyNizCo1-y-z, 0≤y
Y+z≤1 < of≤1,0≤z≤1,0, due to have both specific discharge capacity is high, operating voltage range is wide, thermal stability is good,
Many advantages, such as at low cost is considered as a kind of novel anode material for meeting next-generation LIB growth requirement.However it is practical
Still face structural instability, the problems such as cyclical stability is poor, these are related with rich lithium material body phase and table/interface physicochemical property.
Due to rich lithium material during initial charge there are lattice oxygen evolution, lead to its crystal structure in subsequent charge and discharge process
It destroys, while the acidic materials that the decomposition of organic electrolyte generates can corrode positive electrode, lead to its cycle performance ratio
It is poor.In view of the above-mentioned problems, people have carried out the element doping and the positive material of improvement for the purpose of a large amount of optimization material crystal structures
Expect the research work of table/interface physicochemical property.As Li [Qi Li, Guangshe Li, Chaochao Fu, Dong Luo,
Jianming Fan, and Liping Li, K+-doped Li1.2Mn0.54Co0.13Ni0.13O2: A Novel Cathode
Material With An Enhanced Cycling Stability For Lithium-ion Batteries. J. ACS
Applied materials & interfaces, 2014,6 (13): 10330-10341] et al. by rich lithium ternary just
Pole material Li1.2Mn0.54Ni0.13Co0.13O2Carry out K+Doping, the migration of the formation and Mn that effectively slow down lithium vacancy are led
It causes layer structure to change to spinel structure, improves the cycle performance of material.For another example Xia [Qingbing Xia, Xinfu
Zhao, Mingquan Xu, Zhengping Ding, Jiatu Liu, Libao Chen, Douglas G. lvey,
and Weifeng Wei, A Li-rich Layered@ Spinel@ Carbon heterostructured cathode
material for high capacity and high rate lithium-ion batteries fabricated via
an in situ synchronous carbonization-reduction method. Journal of Materials
Chemistry A, 2015,3 (7): 3995-4003] et al. by 0.33Li2MnO3·0.67Li[Mn1/3Ni1/3Co1/3]
O2Surface coats one layer of dopamine condensate, forms spinel structure and carbon coating layer on positive electrode surface after heat treatment,
Significantly improve the circulation and high rate performance of material.But that there are sintering temperatures is higher for the method, and the carbonizing degree of dopamine is not easy
Control, and the limited electrical conductivity etc. of pyrolytic carbon.
In view of the above-mentioned problems, that the present invention provides a kind of experimental procedures is easily-controllable, can effective stabilizing lithium rich positive electrode body phase
The method of modifying and modified lithium-rich anode material of structure and surface and interface physicochemical property.
Summary of the invention
It is an object of that present invention to provide a kind of K ion dopings and high-voltage spinel/carbon double-coating lithium-rich anode material
Material and preparation method thereof, higher to solve existing sintering temperature, the carbonizing degree of dopamine is not easy to control, and pyrolytic carbon
The technical problems such as limited electrical conductivity.
To achieve the above object, the present invention provides a kind of K ion dopings and high-voltage spinel/carbon double-coating richness
Lithium anode material, nucleome including K modification by ion-doping and the high-voltage spinel/carbon double-contracting for being coated on core surface are covered
Layer；The structural formula of nucleome are as follows: Li1.2-xKxMn0.6-yNi0.2-yCo2yO2, wherein x=0.00-0.1, y=0.00-0.05；High voltage point
In spar/carbon two-coat: the group of high-voltage spinel layer is divided into Li1-xKxMn1.5-yNi0.5-yCo2yO4, wherein x=0.0-0.2,
y=0.0-0.1；Carbon coating layer is the composite construction of dopamine condensate pyrolytic carbon and redox graphene, high voltage appearance point
Lattice oxygen evolution is not present in spar stable structure in 2.0-4.8V voltage range.
Further improvement as material of the invention:
High-voltage spinel and carbon two-coat with a thickness of 3-15nm；Redox graphene accounts for carbon packet in carbon coating layer
The 0.1wt.%-5wt.% of coating gross mass.
As a general technical idea, the present invention also provides a kind of K ion doping and high-voltage spinel/carbon are double-deck
The preparation method of the lithium-rich anode material of cladding, comprising the following steps:
S1: taking the nitrate of lithium, nickel, cobalt, manganese and potassium, and citric acid is added as complexing agent and is made into metal mixed salt solution；
By metal mixed salt solution by spray drying prepare precursor, by precursor progress high temperature sintering be prepared K from
The lithium-rich anode material of sub- doping vario-property, as nucleome；
S2: dopamine condensate is coated in core surface, obtains the lithium-rich anode material of dopamine condensate cladding；
S3: the lithium-rich anode material surface after dopamine condensate cladding is coated into graphene oxide, obtains material F；
S4: material F is sintered, to prepare K ion doping and the rich lithium of high-voltage spinel/carbon double-coating
Positive electrode.
Preferably, step S2, comprising the following steps: nucleome is added to the trishydroxymethylaminomethane of pH=7.5 ~ 11.0
(Tris) in buffer solution, nucleome additional amount is to be added in every 100ml trishydroxymethylaminomethane buffer solution (10mmol/L)
0.01-10g；The ultrasonic treatment preferred 1h of 0.1-2h() Dopamine hydrochloride is added afterwards, the additional amount of Dopamine hydrochloride is every 100ml tri-
0.01-3g is added in hydroxymethyl aminomethane buffer solution；0.1-36h is continuously stirred, dopamine condensate is centrifugally separating to obtain
The lithium-rich anode material of cladding.
Preferably, the step of graphene oxide is coated in step S3 are as follows: the lithium-rich anode material for coating dopamine condensate
Material is added in graphene oxide dispersion, is stirred and is evaporated under 30-95 DEG C (preferably 80 DEG C), obtains material F.
Preferably, the mass fraction of the graphene oxide in graphene oxide dispersion is 0.1wt% ~ 5wt%.
Preferably, the sintering temperature in step S4 is 300 DEG C ~ 700 DEG C, and sintering time is 0 ~ 420min.
Preferably, the amount of the K ion of step S1 is Li+0mol% ~ 8mol% of molal quantity.
As a general technical idea, the present invention also provides a kind of lithium battery anode, including positive electrode, positive materials
Material is above-mentioned K ion doping and high-voltage spinel/carbon double-coating lithium-rich anode material.
And a kind of lithium battery, lithium battery include above-mentioned lithium battery anode.
The invention has the following advantages:
1, K ion doping of the invention and high-voltage spinel/carbon double-coating lithium-rich anode material, appropriate K ion
Introducing can effectively inhibit transformation of the lithium-rich anode material course of work sandwich to spinel structure, significantly improve richness
The problem of mean voltage that discharges in the lithium anode material course of work is decayed.High-voltage spinel clad can be used as lithium-rich anode
Material lattice oxygen evolution inhibition layer, effectively inhibit in its charging process the release of Lattice Oxygen and thus caused by structural instability, electricity
The problems such as chemical property decaying and battery flatulence.
2, K ion doping of the invention and high-voltage spinel/carbon double-coating lithium-rich anode material, compared to rich lithium
Positive electrode matrix has quickly three-dimensional lithium ion conduction characteristic and higher by the high-voltage spinel material of constituent optimization
Electronic conductance.The design of high-voltage spinel/carbon double-coating system can dramatically increase the electricity on lithium-rich anode material surface
Son-lithium ion conductance, and then its surface electrochemistry reactivity is greatly improved, improve the chemical properties such as its multiplying power；Carbon coating
Layer corrosion of the electrolyte middle acid substance to positive active material can be effectively relieved, prevent transition-metal cation dissolution and
The formation of surface SEI film improves modified material surface texture stability, and then is obviously improved its cycle performance.
3, the preparation method of K ion doping of the invention and high-voltage spinel/carbon double-coating lithium-rich anode material,
Modification procedure is easily-controllable, can significantly improve lithium-rich anode material chemical property.
Other than objects, features and advantages described above, there are also other objects, features and advantages by the present invention.
Below with reference to accompanying drawings, the present invention is described in further detail.
Detailed description of the invention
The attached drawing constituted part of this application is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is rich lithium manganese material Li in the embodiment of the present invention 11.2Mn0.54Ni0.13Co0.13O2Nano particle doping and cladding
Modified XRD diagram (original sample: OLO, modified sample: K+- OLO@spinel@carbon@G)；
Fig. 2 is rich lithium manganese material Li in the embodiment of the present invention 11.2Mn0.54Ni0.13Co0.13O2Nano particle doping and cladding
Modified SEM schemes (a:OLO, b:K+- OLO@spinel@carbon@G) and TEM figure (c:OLO, d:K+-OLO@
spinel@carbon@G, e: K+- OLO@spinel@carbon@Graphene)；
Fig. 3 is rich lithium manganese material Li in the embodiment of the present invention 11.2Mn0.54Ni0.13Co0.13O2Nano particle doping and cladding
Modified high rate performance；
Fig. 4 is rich lithium manganese material Li in the embodiment of the present invention 11.2Mn0.54Ni0.13Co0.13O2Nano particle doping and cladding
Modified cycle performance.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but protection scope of the present invention is not limited to example in detail below.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Unless otherwise specified, hereinafter used any raw material, reagent etc. are commercially available or can pass through
Known method prepares.
Embodiment 1:
K+Doping and dopamine condensate and graphene collaboration covered composite yarn modification application are in lithium-rich manganese-based tertiary cathode
Material Li1.2Mn0.54Ni0.13Co0.13O2, it is prepared by following steps:
(1) K is taken+Molal quantity is about Li+The nitrate of molal quantity 1% is added to above-mentioned stoichiometric ratio lithium, nickel, cobalt and manganese nitre
In acid salt solution, suitable citric acid is added as complexing agent, is spray-dried after mixing evenly to its dissolution, obtains forerunner
Body powder；
(2) above-mentioned precursor is sintered at 950 DEG C 10h and obtains K+The rich lithium tertiary cathode material powder of doping vario-property
Body, as nucleome；
(3) the above-mentioned K of 1g is taken+The lithium-rich anode material powder of doping vario-property is added to 10mmol/LTris-HCL buffer solution
100ml(PH=8.5) in be stirred by ultrasonic 1h.Then 6h is continuously stirred after 0.3g Dopamine hydrochloride being added, filtering drying obtains DOPA
The lithium-rich anode material of amine condensate cladding；
(4) lithium-rich anode material after dopamine condensate cladding in step (3) is added to 100mL graphene oxide point
In dispersion liquid (0.3mg/mL), stirring is evaporated at 80 DEG C；
(5) 2 h will be calcined under the conditions of material obtained in step (4) in air 350 DEG C, wherein heating rate is 5
DEG C/min, and above-mentioned crystal structure can be prepared and stablized, the high performance rich lithium three with good lithium ion and electronic conductance
First positive electrode.
This method of modifying known to the XRD spectrum of Fig. 1 does not influence the phase structure of material, has later by dopamine is modified
The formation of Spinel；In conjunction with the SEM and TEM figure in Fig. 2 it can be seen that foring one layer of 8nm or so on positive electrode surface
Even carbon coating layer；It can be seen that modified sample in the case where charge-discharge magnification is 1C from the high rate performance of Fig. 3 to mention than original sample
Rise 45mAh/g；Fig. 4 be before modified after cycle performance figure, it can be found that modified sample recycle at 0.5C 65 enclose after hold
Amount is maintained at 220.8 mAh/g, and more original 150.5 mAh/g of sample improves 70.3 mAh/g；Show side provided by the present invention
Method can effective stabilizing lithium rich material bulk structure, improve its table/interface physicochemical property, high performance richness can be prepared
Lithium anode material.
Embodiment 2:
K+Doping and dopamine condensate and graphene collaboration covered composite yarn modification application are in lithium-rich manganese-based anode material
Li1.2Mn0.6Ni0.2O2, it is prepared by following steps:
(1) K is taken+Molal quantity is about Li+The nitrate of molal quantity 0.5% is added to above-mentioned stoichiometric ratio lithium, nickel, cobalt and manganese
In nitrate solution, suitable citric acid is added as complexing agent, is spray-dried after mixing evenly to its dissolution, before obtaining
Drive body powder；
(2) above-mentioned precursor is sintered at 950 DEG C 10h and obtains K+The lithium-rich anode material of doping vario-property；
(3) the above-mentioned K of 1g is taken+The lithium-rich anode material powder of doping vario-property is added to 10mmol/LTris-HCL buffer solution
100ml(PH=8.0) in be stirred by ultrasonic 1h.Then 10h is continuously stirred after 0.3g Dopamine hydrochloride being added, filtering drying obtains more
The lithium-rich anode material of bar amine condensate cladding；
(4) lithium-rich anode material after dopamine condensate cladding in step (3) is added to 100mL graphene oxide point
In dispersion liquid (0.3mg/mL), stirring is evaporated at 80 DEG C；
(5) by the 450 DEG C of calcining 30min in air of material obtained in step (4), wherein heating rate be 5 DEG C/
min。
Embodiment 3:
K+Doping and dopamine condensate and graphene collaboration covered composite yarn modification application are in lithium-rich manganese-based anode material
Li1.2Mn1.5Ni0.5O2, it is prepared by following steps:
(1) K is taken+Molal quantity is about Li+The nitrate of molal quantity 0.8% is added to above-mentioned stoichiometric ratio lithium, nickel, cobalt and manganese
In nitrate solution, suitable citric acid is added as complexing agent, is spray-dried after mixing evenly to its dissolution, before obtaining
Drive body powder；
(2) above-mentioned precursor is sintered at 950 DEG C 10h and obtains K+The rich lithium tertiary cathode material of doping vario-property；
(3) the above-mentioned K of 1g is taken+The lithium-rich anode material powder of doping vario-property is added to 10mmol/LTris-HCL buffer solution
100ml(PH=8.3) in be stirred by ultrasonic 1h.Then 8h is continuously stirred after 0.3g Dopamine hydrochloride being added, filtering drying obtains DOPA
The lithium-rich anode material of amine condensate cladding；
(4) lithium-rich anode material after dopamine condensate cladding in step (3) is added to 100mL graphene oxide point
In dispersion liquid (0.3mg/mL), stirring is evaporated at 80 DEG C；
(5) by the 500 DEG C of calcining 10min in air of material obtained in step (4), wherein heating rate be 10 DEG C/
Min, can prepare this crystal structure stablizes, the high performance lithium-rich anode material with good lithium ion and electronic conductance
Material.
Embodiment 4:
Lithium battery, the lithium battery anode of the lithium battery, positive electrode are the K ion doping and high voltage point crystalline substance of embodiment 1
Stone/carbon double-coating lithium-rich anode material.
In summary, the present invention can effective stabilizing lithium rich material bulk structure, it is physical and chemical special to improve its table/interface
Property, high performance lithium-rich anode material and lithium battery anode and lithium battery can be prepared.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of K ion doping and high-voltage spinel/carbon double-coating lithium-rich anode material, which is characterized in that including K from
The nucleome of sub- doping vario-property and the high-voltage spinel/carbon two-coat for being coated on core surface；
The structural formula of the nucleome are as follows: Li1.2-xKxMn0.6-yNi0.2-yCo2yO2, wherein x=0.00-0.1, y=0.00-0.05；
In the high-voltage spinel/carbon two-coat: the group of high-voltage spinel layer is divided into Li1-xKxMn1.5-yNi0.5- yCo2yO4, wherein x=0.0-0.2, y=0.0-0.1；Carbon coating layer is dopamine condensate pyrolytic carbon and redox graphene
Composite construction.
2. lithium-rich anode material according to claim 1, which is characterized in that the high-voltage spinel and carbon two-coat
With a thickness of 3-15nm；Redox graphene accounts for the 0.1wt.%-5wt.% of carbon coating layer gross mass in the carbon coating layer.
3. a kind of K ion doping as claimed in claim 1 or 2 and high-voltage spinel/carbon double-coating lithium-rich anode material
The preparation method of material, comprising the following steps:
S1: taking the nitrate of lithium, nickel, cobalt, manganese and potassium, and citric acid is added as complexing agent and is made into metal mixed salt solution；By institute
State metal mixed salt solution by spray drying prepare precursor, by precursor progress high temperature sintering be prepared K from
The lithium-rich anode material of sub- doping vario-property, as nucleome；
S2: dopamine condensate is coated in core surface, obtains the lithium-rich anode material of dopamine condensate cladding；
S3: the lithium-rich anode material surface after dopamine condensate cladding is coated into graphene oxide, obtains material F；
S4: material F is sintered, to prepare K ion doping and high-voltage spinel/carbon double-coating lithium-rich anode
Material.
4. preparation method according to claim 3, which is characterized in that the step S2, comprising the following steps:
Nucleome is added in the trishydroxymethylaminomethane buffer solution of pH=7.5 ~ 11.0, nucleome additional amount is every 100ml tri-
0.01-10g is added in hydroxymethyl aminomethane buffer solution；Dopamine hydrochloride, hydrochloric acid DOPA is added after ultrasonic treatment 0.1-2h
The additional amount of amine is that 0.01-3g is added in every 100ml trishydroxymethylaminomethane buffer solution；0.1-36h is continuously stirred, is centrifuged
The lithium-rich anode material of isolated dopamine condensate cladding.
5. preparation method according to claim 3, which is characterized in that the step of coating graphene oxide in the step S3
Are as follows: the lithium-rich anode material that dopamine condensate coats is added in graphene oxide dispersion, stirs and steams at 30-95 DEG C
It is dry, obtain material F.
6. preparation method according to claim 5, which is characterized in that the graphite oxide in the graphene oxide dispersion
The mass fraction of alkene is 0.1wt% ~ 5wt%.
7. preparation method according to claim 3, which is characterized in that sintering temperature in the step S4 is 300 DEG C ~
700 DEG C, sintering time is 0 ~ 420min.
8. the preparation method according to any one of claim 3 to 7, which is characterized in that the amount of K ion described in step S1
For Li+0mol% ~ 8mol% of molal quantity.
9. a kind of lithium battery anode, including positive electrode, which is characterized in that the positive electrode is of any of claims 1 or 2
K ion doping and high-voltage spinel/carbon double-coating lithium-rich anode material.
10. a kind of lithium battery, which is characterized in that the lithium battery includes lithium battery anode as claimed in claim 9.
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| CN107394156A (en) * | 2017-07-19 | 2017-11-24 | 长沙矿冶研究院有限责任公司 | A kind of method of modifying and its modified anode material of the lithium-rich manganese-based anode material for lithium-ion batteries based on organic matter ammoniacal liquor |
| CN108336318B (en) * | 2017-12-12 | 2020-09-01 | 天能帅福得能源股份有限公司 | Molybdenum/fluorine co-doped and spinel in-situ coated lithium-rich cathode material and preparation method thereof |
| CN108336316B (en) * | 2017-12-12 | 2020-09-01 | 天能帅福得能源股份有限公司 | MOFs surface modification-based lithium-rich cathode material and preparation method thereof |
| CN112786875B (en) * | 2020-12-30 | 2023-02-14 | 华南理工大学 | Potassium ion doped carbon-coated lithium-rich ternary positive electrode material and preparation method and application thereof |
| CN113603141B (en) * | 2021-08-02 | 2022-09-13 | 中国科学院过程工程研究所 | Composite positive electrode material, preparation method and application thereof |
| CN113903919A (en) * | 2021-09-29 | 2022-01-07 | 中国人民解放军国防科技大学 | Modified high-voltage positive electrode material and preparation method and application thereof |
| CN114023953A (en) * | 2021-11-03 | 2022-02-08 | 惠州亿纬锂能股份有限公司 | Modified lithium iron manganese phosphate cathode material and preparation method and application thereof |
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