CN106299342A - Lithium-rich anode material of K ion doping and high-voltage spinel/carbon double-coating and preparation method thereof - Google Patents
Lithium-rich anode material of K ion doping and high-voltage spinel/carbon double-coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses lithium-rich anode material of a kind of K ion doping and high-voltage spinel/carbon double-coating and preparation method thereof.This lithium-rich anode material includes the nucleome of K modification by ion-doping and is coated on the high-voltage spinel/carbon two-coat of core surface；Nucleome is: Li1.2‑xKxMn0.6‑yNi0.2‑yCo2yO2, wherein x=0.00 0.1, y=0.00 0.05；The component of high-voltage spinel/carbon two-coat high voltage appearance spinel layer is Li1‑xKxMn1.5‑ yNi0.5‑yCo2yO4, wherein x=0.0 0.2, y=0.0 0.1；Carbon coating layer is dopamine polymer pyrolytic carbon and the composite construction of redox graphene.Its preparation method includes the nucleome being prepared K modification by ion-doping by spray drying technology, at its Surface coating dopamine polymer, carry out the cladding of graphene oxide on this basis, by follow-up sintering, thus prepare K ion doping and the lithium-rich anode material of high-voltage spinel/carbon double-coating.It is easily-controllable that the present invention has modification procedure, 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 field, particularly relate to have K ion doping and height electricity concurrently
Lithium-rich anode material of pointing spar/carbon double-coating and preparation method thereof, lithium battery anode and lithium battery.
Background technology
The energy and environmental crisis have become puzzlement very important two problems of society, therefore to high performance energy
Store and the development of conversion equipment is had higher requirement.It is close that lithium ion battery has specific energy/power as secondary cell
The advantages such as degree is high, have extended cycle life, memory-less effect, pollution-free and security performance are good, have on miniaturized electronics
Application widely.The new market demand requires LIB(lithium ion battery of future generation) technology in addition to possessing traditional advantage,
Also there are higher energy/power density, more preferable cyclical stability and lower production and operation cost.Wherein high-performance,
The exploitation of low cost positive electrode is the key that LIB is used practically in the field such as electric automobile 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
≤ 1,0≤z≤1,0 ＜ y+z≤1, due to have concurrently specific discharge capacity height, operating voltage range width, Heat stability is good,
The plurality of advantages such as low cost are considered as a kind of novel anode material meeting LIB growth requirement of future generation.But it is practical
Still facing the problem such as structural instability, cyclical stability difference, these are all relevant with rich lithium material body phase and table/interface physicochemical property.
Owing to rich lithium material exists Lattice Oxygen release during initial charge, cause its crystal structure in follow-up charge and discharge process
Destroying, the acidic materials decomposing generation of organic electrolyte can cause its cycle performance ratio to positive pole material corrosion simultaneously
Poor.For the problems referred to above, people have carried out the element doping for the purpose of a large amount of optimization material crystal structure and have improved positive pole material
The research work of material 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 room is led
Cause layer structure to change to spinel structure, improve the cycle performance of material.And for 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]
O2One layer of dopamine polymer of Surface coating, defines spinel structure and carbon coating layer on positive electrode surface after heat treatment,
Significantly improve circulation and the high rate performance of material.But it is higher that the method exists sintering temperature, the carbonizing degree of dopamine is difficult to
Control, and the limited electrical conductivity of pyrolytic carbon etc..
For the problems referred to above, the invention provides a kind of experimental procedure easily-controllable, can effective stabilizing lithium rich positive electrode body phase
Structure and the method for modifying of surface and interface physicochemical property and modified lithium-rich anode material.
Summary of the invention
Present invention aim at providing a kind of K ion doping and the lithium-rich anode material of high-voltage spinel/carbon double-coating
Material and preparation method thereof, higher to solve existing sintering temperature, the carbonizing degree of dopamine is wayward, and pyrolytic carbon
The technical problems such as limited electrical conductivity.
For achieving the above object, the invention provides a kind of K ion doping and the richness of high-voltage spinel/carbon double-coating
Lithium anode material, including the nucleome of K modification by ion-doping and be coated on the high-voltage spinel/carbon double-contracting of core surface and cover
Layer；The structural formula of nucleome is: 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 component of high-voltage spinel layer is Li1-xKxMn1.5-yNi0.5-yCo2yO4, wherein x=0.0-0.2,
y=0.0-0.1；Carbon coating layer is dopamine polymer pyrolytic carbon and the composite construction of redox graphene, its high voltage appearance point
Spar is stable in 2.0-4.8V voltage range inner structure, there is not Lattice Oxygen release.
Further improvement as the material of the present invention:
The thickness of high-voltage spinel and carbon two-coat is 3-15nm；In carbon coating layer, redox graphene accounts for carbon coating layer
The 0.1wt.%-5wt.% of gross mass.
As total technology design, present invention also offers a kind of K ion doping and high-voltage spinel/carbon is double-deck
The preparation method of the lithium-rich anode material of cladding, comprises the following steps:
S1: take the nitrate of lithium, nickel, cobalt, manganese and potassium, adds citric acid and is made into slaine mixed solution as chelating agent；By gold
Belong to mixed salt solution and prepare precursor by spray drying, precursor is carried out high temperature sintering and prepares K ion and mix
The lithium-rich anode material of miscellaneous modification, as nucleome；
S2: be coated with dopamine polymer at core surface, obtains the lithium-rich anode material of dopamine polymer cladding；
S3: the lithium-rich anode material Surface coating graphene oxide after being coated with by dopamine polymer, obtains material F；
S4: material F is sintered, thus prepare K ion doping and the lithium-rich anode of high-voltage spinel/carbon double-coating
Material.
Preferably, step S2, comprise the following steps: nucleome is joined the trishydroxymethylaminomethane of pH=7.5 ~ 11.0
(Tris), in buffer solution, nucleome addition is to add in every 100ml trishydroxymethylaminomethane buffer solution (10mmol/L)
0.01-10g；The preferred 1h of supersound process 0.1-2h() add dopamine hydrochloride afterwards, the addition of dopamine hydrochloride is every 100ml tri-
Hydroxymethyl aminomethane buffer solution adds 0.01-3g；Continuous stirring 0.1-36h, is centrifugally separating to obtain dopamine polymer
The lithium-rich anode material of cladding.
Preferably, the step being coated with graphene oxide in step S3 is: the lithium-rich anode material being coated with by dopamine polymer
Material joins in graphene oxide dispersion, stirs and is evaporated, obtain material F under 30-95 DEG C (preferably 80 DEG C).
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% ~ the 8mol% of molal quantity.
As total technology design, present invention also offers a kind of lithium battery anode, including positive electrode, positive pole material
Material is above-mentioned K ion doping and the lithium-rich anode material of high-voltage spinel/carbon double-coating.
And one lithium battery, lithium battery includes above-mentioned lithium battery anode.
The method have the advantages that
1, the K ion doping of the present invention and the lithium-rich anode material of high-voltage spinel/carbon double-coating, drawing of appropriate K ion
Enter effectively to suppress lithium-rich anode material work process sandwich to the transformation of spinel structure, just significantly improve rich lithium
The problem that the mean voltage that discharges during the material work of pole is decayed.High-voltage spinel clad can be as lithium-rich anode material
Lattice Oxygen release inhibition layer, effectively suppresses release and the structural instability thus caused, the electrochemistry of Lattice Oxygen in its charging process
The problems such as performance degradation and battery flatulence.
2, the K ion doping of the present invention and the lithium-rich anode material of high-voltage spinel/carbon double-coating, compared to rich lithium
Positive electrode matrix, the high-voltage spinel material through constituent optimization has the most three-dimensional lithium ion conduction characteristic and Geng Gao
Electronic conductance.High-voltage spinel/carbon double-coating system be designed to 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 is coated with
Layer can effectively alleviate the corrosion to positive active material of the electrolyte middle acid substance, prevent transition-metal cation dissolving and
The formation of surface SEI film, improves material modified surface texture stability, and then is obviously improved its cycle performance.
3, the preparation method of the lithium-rich anode material of the K ion doping of the present invention and high-voltage spinel/carbon double-coating,
Modification procedure is easily-controllable, can significantly improve lithium-rich anode material chemical property.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to accompanying drawings, the present invention is further detailed explanation.
Accompanying drawing explanation
The accompanying drawing of the part constituting the application is used for providing a further understanding of the present invention, and the present invention's is schematic real
Execute example and illustrate for explaining the present invention, being not intended that inappropriate limitation 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 coating modification
XRD figure (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 coating modification
SEM scheme (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 coating modification
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 coating modification
Cycle performance.
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with Figure of description and preferred embodiment, the present invention is made more complete
Face, describe meticulously, but protection scope of the present invention is not limited to example in detail below.
Unless otherwise defined, the implication that all technical term used hereinafter is generally understood that with those skilled in the art
Identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the present invention
Protection domain.
Unless otherwise specified, hereinafter used any raw material, reagent etc. are all commercially available and maybe can pass through
Known method prepares.
Embodiment 1:
K+Doping and dopamine polymer and Graphene work in coordination with covered composite yarn modification application in lithium-rich manganese-based tertiary cathode material
Li1.2Mn0.54Ni0.13Co0.13O2, prepared by following steps:
(1) K is taken+Molal quantity is about Li+The nitrate of molal quantity 1% joins above-mentioned stoichiometric proportion lithium, nickel, cobalt and manganese nitric acid
In saline solution, add appropriate citric acid as chelating agent, be spray-dried after it dissolves and stirs, obtain presoma
Powder body；
(2) above-mentioned precursor is sintered at 950 DEG C 10h and obtain K+The rich lithium tertiary cathode material powder body of doping vario-property, makees
For nucleome；
(3) the above-mentioned K of 1g is taken+The lithium-rich anode material powder body of doping vario-property joins 10mmol/LTris-HCL buffer solution
Ultrasonic agitation 1h in 100ml(PH=8.5).Being subsequently adding continuous stirring 6h after 0.3g dopamine hydrochloride, filtering drying obtains DOPA
The lithium-rich anode material of amine polymer cladding；
(4) lithium-rich anode material after dopamine polymer cladding in step (3) is joined 100mL graphene oxide dispersion
(0.3mg/mL), in, at 80 DEG C, stirring is evaporated；
(5) 2 h will be calcined under the conditions of the material obtained in step (4) in atmosphere 350 DEG C, wherein programming rate be 5 DEG C/
Min, can prepare above-mentioned crystal structure stable, just has the high performance rich lithium ternary of good lithium ion and electronic conductance
Pole material.
This method of modifying knowable to the XRD figure of Fig. 1 is composed does not affects the phase structure of material, has after dopamine modification
The formation of Spinel；Can be seen that in conjunction with SEM and the TEM figure in Fig. 2 and define one layer of about 8nm on positive electrode surface all
Even carbon coating layer；From the high rate performance of Fig. 3 it can be seen that modified sample carries than original sample charge-discharge magnification is 1C
Rise 45mAh/g；Fig. 4 be before modified after cycle performance figure, it appeared that modified sample circulate under 0.5C 65 circle after hold
Amount is maintained at 220.8 mAh/g, more original sample 150.5 mAh/g and improves 70.3 mAh/g；Show side provided by the present invention
Method can the bulk structure of effective stabilizing lithium rich material, improve its table/interface physicochemical property, high performance richness can be prepared
Lithium anode material.
Embodiment 2:
K+Doping and dopamine polymer and Graphene work in coordination with covered composite yarn modification application in lithium-rich manganese-based anode material
Li1.2Mn0.6Ni0.2O2, prepared by following steps:
(1) K is taken+Molal quantity is about Li+The nitrate of molal quantity 0.5% joins above-mentioned stoichiometric proportion lithium, nickel, cobalt and manganese nitre
In acid salt solution, add appropriate citric acid as chelating agent, be spray-dried after it dissolves and stirs, obtain forerunner
Body powder body；
(2) above-mentioned precursor is sintered at 950 DEG C 10h and obtain 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 body of doping vario-property joins 10mmol/LTris-HCL buffer solution
Ultrasonic agitation 1h in 100ml(PH=8.0).Being subsequently adding continuous stirring 10h after 0.3g dopamine hydrochloride, filtering drying obtains many
The lithium-rich anode material of bar amine polymer cladding；
(4) lithium-rich anode material after dopamine polymer cladding in step (3) is joined 100mL graphene oxide dispersion
(0.3mg/mL), in, at 80 DEG C, stirring is evaporated；
(5) the material 450 DEG C of calcining 30min in atmosphere that will obtain in step (4), wherein programming rate is 5 DEG C/min.
Embodiment 3:
K+Doping and dopamine polymer and Graphene work in coordination with covered composite yarn modification application in lithium-rich manganese-based anode material
Li1.2Mn1.5Ni0.5O2, prepared by following steps:
(1) K is taken+Molal quantity is about Li+The nitrate of molal quantity 0.8% joins above-mentioned stoichiometric proportion lithium, nickel, cobalt and manganese nitre
In acid salt solution, add appropriate citric acid as chelating agent, be spray-dried after it dissolves and stirs, obtain forerunner
Body powder body；
(2) above-mentioned precursor is sintered at 950 DEG C 10h and obtain 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 body of doping vario-property joins 10mmol/LTris-HCL buffer solution
Ultrasonic agitation 1h in 100ml(PH=8.3).Being subsequently adding continuous stirring 8h after 0.3g dopamine hydrochloride, filtering drying obtains DOPA
The lithium-rich anode material of amine polymer cladding；
(4) lithium-rich anode material after dopamine polymer cladding in step (3) is joined 100mL graphene oxide dispersion
(0.3mg/mL), in, at 80 DEG C, stirring is evaporated；
(5) the material 500 DEG C of calcining 10min in atmosphere that will obtain in step (4), wherein programming rate is 10 DEG C/min,
This crystal structure can be prepared stable, there is the high performance lithium-rich anode material of good lithium ion and electronic conductance.
Embodiment 4:
Lithium battery, the lithium battery anode of this lithium battery, positive electrode is K ion doping and the high-voltage spinel/carbon of embodiment 1
The lithium-rich anode material of double-coating.
In summary, the present invention can the bulk structure of effective stabilizing lithium rich material, improve its table/interface physics and chemistry special
Property, can prepare high performance lithium-rich anode material, and lithium battery anode and lithium battery.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, that is made any repaiies
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a K ion doping and the lithium-rich anode material of high-voltage spinel/carbon double-coating, it is characterised in that include K from
The nucleome of sub-doping vario-property and be coated on the high-voltage spinel/carbon two-coat of core surface；
The structural formula of described nucleome is: Li1.2-xKxMn0.6-yNi0.2-yCo2yO2, wherein x=0.00-0.1, y=0.00-0.05；
In described high-voltage spinel/carbon two-coat: the component of high-voltage spinel layer is Li1-xKxMn1.5-yNi0.5- yCo2yO4, wherein x=0.0-0.2, y=0.0-0.1；Carbon coating layer is dopamine polymer pyrolytic carbon and redox graphene
Composite construction.
Lithium-rich anode material the most according to claim 1, it is characterised in that described high-voltage spinel and carbon two-coat
Thickness be 3-15nm；In described carbon coating layer, redox graphene accounts for the 0.1wt.%-5wt.% of carbon coating layer gross mass.
3. a K ion doping as claimed in claim 1 or 2 and the lithium-rich anode material of high-voltage spinel/carbon double-coating
The preparation method of material, comprises the following steps:
S1: take the nitrate of lithium, nickel, cobalt, manganese and potassium, adds citric acid and is made into slaine mixed solution as chelating agent；By institute
State slaine mixed solution and prepare precursor by spray drying, precursor is carried out high temperature sintering prepare K from
The lithium-rich anode material of sub-doping vario-property, as nucleome；
S2: be coated with dopamine polymer at core surface, obtains the lithium-rich anode material of dopamine polymer cladding；
S3: the lithium-rich anode material Surface coating graphene oxide after being coated with by dopamine polymer, obtains material F；
S4: material F is sintered, thus prepare K ion doping and the lithium-rich anode of high-voltage spinel/carbon double-coating
Material.
Preparation method the most according to claim 3, it is characterised in that described step S2, comprises the following steps:
Being joined by nucleome in the trishydroxymethylaminomethane buffer solution of pH=7.5 ~ 11.0, nucleome addition is every 100ml tri-
Hydroxymethyl aminomethane buffer solution adds 0.01-10g；Dopamine hydrochloride, hydrochloric acid DOPA is added after supersound process 0.1-2h
The addition of amine is addition 0.01-3g in every 100ml trishydroxymethylaminomethane buffer solution；Continuous stirring 0.1-36h, centrifugal
The lithium-rich anode material of isolated dopamine polymer cladding.
Preparation method the most according to claim 3, it is characterised in that be coated with the step of graphene oxide in described step S3
For: joining in graphene oxide dispersion by the lithium-rich anode material that dopamine polymer is coated with, at 30-95 DEG C, stirring is steamed
Dry, obtain material F.
Preparation method the most according to claim 5, it is characterised in that the graphite oxide in described graphene oxide dispersion
The mass fraction of alkene is 0.1wt% ~ 5wt%.
Preparation method the most according to claim 3, it is characterised in that the sintering temperature in described step S4 is 300 DEG C ~
700 DEG C, sintering time is 0 ~ 420min.
8. according to the preparation method according to any one of claim 3 to 7, it is characterised in that the amount of the K ion described in step S1
For Li+0mol% ~ the 8mol% of molal quantity.
9. a lithium battery anode, including positive electrode, it is characterised in that described positive electrode is described in claim 1 or 2
K ion doping and the lithium-rich anode material of high-voltage spinel/carbon double-coating.
10. a lithium battery, it is characterised in that described lithium battery includes the lithium battery anode described in claim 9.
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Cited By (7)
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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 |
| CN108336316A (en) * | 2017-12-12 | 2018-07-27 | 浙江天能能源科技股份有限公司 | A kind of lithium-rich anode material and preparation method thereof being modified based on the surfaces MOFs |
| CN108336318A (en) * | 2017-12-12 | 2018-07-27 | 浙江天能能源科技股份有限公司 | A kind of molybdenum/fluorin-doped and spinelle in-stiu coating lithium-rich anode material and preparation method thereof |
| CN112786875A (en) * | 2020-12-30 | 2021-05-11 | 华南理工大学 | Potassium ion doped carbon-coated lithium-rich ternary positive electrode material and preparation method and application thereof |
| CN113603141A (en) * | 2021-08-02 | 2021-11-05 | 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1200581A (en) * | 1997-05-22 | 1998-12-02 | 松下电器产业株式会社 | Non-aqueous electrolyte secondary battery |
| CN101926030A (en) * | 2008-01-28 | 2010-12-22 | 夏普株式会社 | Positive electrode active material, positive electrode, and nonaqueous rechargeable battery |
| CN103418403A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Low-temperature high-load catalyst for olefin ammoxidation reaction |
-
2016
- 2016-10-28 CN CN201610960159.7A patent/CN106299342B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1200581A (en) * | 1997-05-22 | 1998-12-02 | 松下电器产业株式会社 | Non-aqueous electrolyte secondary battery |
| CN101926030A (en) * | 2008-01-28 | 2010-12-22 | 夏普株式会社 | Positive electrode active material, positive electrode, and nonaqueous rechargeable battery |
| CN103418403A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Low-temperature high-load catalyst for olefin ammoxidation reaction |
Non-Patent Citations (2)
| Title |
|---|
| QI LI，ET AL.: "K doped Li1.2Mn0.54Co0.13Ni0....for lithium-ion batteries", 《APPLIED MATERIALS&INTERFACES》 * |
| QINGBING XIA，ET AL.: "A Li-rich layered@spinel@Carbon heterostructured cathode material for high capacity and high rate lithium-ion batteries fabricated via an situ synchronous carbonization-reduction method", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (8)
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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 |
| CN108336316A (en) * | 2017-12-12 | 2018-07-27 | 浙江天能能源科技股份有限公司 | A kind of lithium-rich anode material and preparation method thereof being modified based on the surfaces MOFs |
| CN108336318A (en) * | 2017-12-12 | 2018-07-27 | 浙江天能能源科技股份有限公司 | A kind of molybdenum/fluorin-doped and spinelle in-stiu coating lithium-rich anode 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 |
| CN112786875A (en) * | 2020-12-30 | 2021-05-11 | 华南理工大学 | Potassium ion doped carbon-coated lithium-rich ternary positive electrode material and preparation method and application thereof |
| CN113603141A (en) * | 2021-08-02 | 2021-11-05 | 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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