CN107768634A - A kind of ion doping and Surface coating modify anode material for lithium-ion batteries and preparation method thereof jointly - Google Patents
A kind of ion doping and Surface coating modify anode material for lithium-ion batteries and preparation method thereof jointly Download PDFInfo
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- CN107768634A CN107768634A CN201710964287.3A CN201710964287A CN107768634A CN 107768634 A CN107768634 A CN 107768634A CN 201710964287 A CN201710964287 A CN 201710964287A CN 107768634 A CN107768634 A CN 107768634A
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Abstract
The present invention relates to anode material of lithium battery technical field, especially a kind of ion doping and Surface coating modify anode material for lithium-ion batteries and preparation method thereof jointly, by modifying anode active material of lithium ion battery NCM materials jointly using ion doping and with Surface coating, realization carries out modification from NCM material internal to surface, stabilize the internal structure of material, material and lithium ion diffusivity at electrolyte interface are improved again, protective effect also is provided to material, effectively it can reduce in charge and discharge process, the side reaction of material and electrolyte, improve the cyclical stability and high rate performance of lithium ion battery.
Description
Technical field
The present invention relates to anode material of lithium battery technical field, especially a kind of ion doping and Surface coating are modified jointly
Anode material for lithium-ion batteries and preparation method thereof.
Background technology
With greatly developing for energy-accumulating power station and new-energy automobile, the research and development and application of lithium ion battery, welcome at a high speed
The period of development；For the new-energy automobile using lithium ion battery as power producer, its energy density still can not with it is traditional
Fuel-engined vehicle compares favourably so as to low cost, the research and development of the lithium ion battery of high-energy-density, becomes current field of lithium
The focus constantly studied.
Positive electrode is the key components of lithium ion battery, its performance it is whether excellent, largely, determine
The quality of performance of lithium ion battery, in order to obtain the lithium ion battery of high-energy-density, on the one hand can improve work
Voltage, the positive electrode with high specific capacity on the other hand can be selected, as used than traditional cobalt acid lithium or making extensively
LiFePO4 has the nickle cobalt lithium manganate (LiNi of more height ratio capacityxCoyMn1-x-yO2, hereinafter referred to as NCM ternary materials) and material
Material, turn into current focus of attention, and be also most in field of lithium ion battery material development potentiality.But in reality
In the charge and discharge process of border, NCM ternary materials are in thermodynamic instability state with electrolyte, and redox reaction easily occurs,
Cause in NCM materials that into electrolyte, anode structure wrecks part metals ion-solubility, cause battery performance to decline, because
This, improves structural stability of the positive pole NCM ternary materials in charge and discharge process, reduces anti-between NCM materials and electrolyte
Degree is answered, is the key for improving performance of lithium ion battery.
Based on this, this researcher is studied for the performance of lithium ion anode material material, by lithium ion anode
Material carries out moditied processing so that the excellent performance of anode material for lithium-ion batteries, is provided for anode material for lithium-ion batteries
A kind of new approaches.
The content of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention provides a kind of ion doping and Surface coating
Common modification anode material for lithium-ion batteries and preparation method thereof.
It is achieved particular by following technical scheme：
A kind of ion doping and Surface coating modify anode material for lithium-ion batteries jointly, are to use positive electrode active materials
Nb ion dopings so that it forms particulate matter, and uses the bag with quick conducting lithium ions ability on particulate matter surface
Cover agent and be coated on surface of positive electrode active material and form.
Described positive electrode active materials are nickel-cobalt lithium manganate materials.
Described nickel-cobalt lithium manganate material is LiNi0.8Co0.1Mn0.1O2, LiNi0.6Co0.2Mn0.2O2,
LiNi0.5Co0.2Mn0.3O2, LiNi0.4Co0.2Mn0.4O2, LiNi1/3Co1/3Mn1/3O2In one kind.
Described nickel-cobalt lithium manganate material is spheric granules, spherical particle, bar-shaped or sheet.
Described covering 0.035Li2O·BPO4。
Described covering cladding is by the positive electrode active materials table of Nb ion dopings by covering by growth in situ
Layer.
Described uses Nb ion dopings, and metallic element Nb molar content is 0.005~0.2% after doping.
Described covering, after cladding, account for the 0.02~5% of anode material for lithium-ion batteries gross mass.
Described covering cladding, thickness is 5~50nm.
The second purpose of the invention is also to provide above-mentioned ion doping and Surface coating modifies lithium-ion electric jointly
Pond method for preparing anode material, comprises the following steps：
(1) according to positive electrode active materials formula Li (NixCoyMn1-x-y)1-aNbaO2In stoichiometric proportion, weigh nickel salt,
Cobalt salt, manganese salt, lithium salts, Nb compound, are added in deionized water, and add 2.620g citric acids with 500mL deionized waters
With 5.012g ethylene glycol, colloidal sol is made in dissolving, is evaporated as gel, dries, is placed in sintering furnace, is forged at 750-1000 DEG C
6-15h is burnt, is crushed, grinding, obtains Li (NixCoyMn1-x-y)1-aNbaO2Material, wherein, a is 0.005~0.2；Or according to just
Pole active material formula Li (NixCoyMn1-x-y)1-aNbaO2In stoichiometric proportion, weigh nickel salt, cobalt salt, manganese salt, lithium salts, Nb
Compound, be sufficiently mixed uniformly, after the completion of mixing, be placed in sintering furnace, 6-15h calcined at 750-1000 DEG C, crush, grind
Mill, obtains Li (NixCoyMn1-x-y)1-aNbaO2Material, wherein, a is 0.005~0.2；
(2) it is 0.035Li according to chemical formula2O·BPO4Molar ratio weighing lithium source, phosphorus source, the boron source of middle each element, and it is molten
Solution is 0~7 according to volume ratio in second alcohol and water:In 1 mixed liquor mixed, LBP is obtained；The Li that step (1) is obtained again
(NixCoyMn1-x-y)1-aNbaO2Material is added thereto, and stirring, heating evaporation, is obtained solid powder, is placed in calcining furnace, 250
2-6h is calcined at~600 DEG C, obtains (1-m) Li (NixCoyMn1-x-y)1-aNbaO2MLBP lithium ion anode material, wherein m
For 0.02~5.
One or more of the described nickel salt in nickel nitrate, nickel acetate, nickel sulfate.
One or more of the described cobalt salt in cobalt nitrate, cobalt acetate, cobaltous sulfate.
One or more of the described manganese salt in manganese nitrate, manganese acetate, manganese sulfate.
Described lithium salts is selected from the mixing of one or both of lithium hydroxide, lithium carbonate.
One or two kinds of mixing of the described Nb compound in niobium oxide, niobium oxalate.
Lithium source can be lithium metaborate, lithium tetraborate and/or lithium hydroxide；Boron source can be boric acid, lithium metaborate and/or
Lithium tetraborate；Phosphorus source can be phosphoric acid and/or ammonium dihydrogen phosphate.
Compared with prior art, the technique effect of the invention is embodied in：
It is real by modifying anode active material of lithium ion battery-NCM materials jointly using ion doping and with Surface coating
Modification is now carried out from NCM material internal to surface, the internal structure of material is stabilized, improves material and electrolyte circle again
Lithium ion diffusivity at face, also provides protective effect to material, effectively can reduce in charge and discharge process, material and electricity
The side reaction of liquid is solved, improves the cyclical stability and high rate performance of lithium ion battery.
Brief description of the drawings
Fig. 1 is that the invention tri- kinds of materials of pure 622NCM, 622NCM-Nb0.1 and 622NCM-Nb0.1-2LBP make knob
Detain battery after under the conditions of room temperature, 0.2C, 2.8~4.3V first charge-discharge curve.
Fig. 2 is that tri- kinds of materials of pure 811NCM, 811NCM-Nb0.05 and 811NCM-Nb0.05-2LBP of the invention are done
Cycle performance after into button cell under the conditions of room temperature, 2C, 2.8~4.3V.
Fig. 3 is tri- kinds of materials of pure 523NCM, 523NCM-Nb0.05 and 523NCM-Nb0.05-2LBP of the invention
XRD.
Fig. 4 be the invention product 3NCM-Nb0.05-2LBP materials in each element XPS collection of illustrative plates.
Fig. 5 is that the invention tri- kinds of materials of pure 523NCM, 523NCM-Nb0.05 and 523NCM-Nb0.05-2LBP are made
High rate performance after button cell under the conditions of room temperature, 2.8~4.3V.
Embodiment
Limited technical scheme is further, but required with specific embodiment below in conjunction with the accompanying drawings
The scope of protection is not only limited to made description.
In certain embodiments, ion doping and Surface coating modify anode material for lithium-ion batteries jointly, are by positive pole
Active material uses Nb ion dopings so that and it forms particulate matter, and on particulate matter surface using having quick conductive lithium
The covering of ion energy is coated on surface of positive electrode active material and formed.
In certain embodiments, described positive electrode active materials are nickel-cobalt lithium manganate materials.
In certain embodiments, described nickel-cobalt lithium manganate material is LiNi0.8Co0.1Mn0.1O2,
LiNi0.6Co0.2Mn0.2O2, LiNi0.5Co0.2Mn0.3O2, LiNi0.4Co0.2Mn0.4O2, LiNi1/3Co1/3Mn1/3O2In one kind.
In certain embodiments, described nickel-cobalt lithium manganate material is spheric granules, spherical particle, bar-shaped or piece
Shape.
In certain embodiments, described covering 0.035Li2O·BPO4。
In certain embodiments, described covering cladding is by Nb ion dopings by covering by growth in situ
Positive electrode active materials top layer.
In certain embodiments, described use Nb ion dopings, metallic element Nb molar content is 0.005 after doping
~0.2%.
In certain embodiments, described covering, after cladding, account for anode material for lithium-ion batteries gross mass 0.02~
5%.
In certain embodiments, described covering cladding, thickness is 5~50nm.
In certain embodiments, above-mentioned ion doping and Surface coating are also provided and modifies lithium ion cell positive material jointly
Preparation method for material, comprise the following steps：
(1) according to positive electrode active materials formula Li (NixCoyMn1-x-y)1-aNbaO2In stoichiometric proportion, weigh nickel salt,
Cobalt salt, manganese salt, lithium salts, Nb compound, are added in deionized water, and add 2.620g citric acids with 500mL deionized waters
With 5.012g ethylene glycol, colloidal sol is made in dissolving, is evaporated as gel, dries, is placed in sintering furnace, is forged at 750-1000 DEG C
6-15h is burnt, is crushed, grinding, obtains Li (NixCoyMn1-x-y)1-aNbaO2Material, wherein, a is 0.005~0.2；Or according to just
Pole active material formula Li (NixCoyMn1-x-y)1-aNbaO2In stoichiometric proportion, weigh nickel salt, cobalt salt, manganese salt, lithium salts, Nb
Compound, be sufficiently mixed uniformly, after the completion of mixing, be placed in sintering furnace, 6-15h calcined at 750-1000 DEG C, crush, grind
Mill, obtains Li (NixCoyMn1-x-y)1-aNbaO2Material, wherein, a is 0.005~0.2；
(2) it is 0.035Li according to chemical formula2O·BPO4Molar ratio weighing lithium source, phosphorus source, the boron source of middle each element, and it is molten
Solution is 0~7 according to volume ratio in second alcohol and water:In 1 mixed liquor mixed, LBP is obtained；The Li that step (1) is obtained again
(NixCoyMn1-x-y)1-aNbaO2Material is added thereto, and stirring, heating evaporation, is obtained solid powder, is placed in calcining furnace, 250
2-6h is calcined at~600 DEG C, obtains (1-m) Li (NixCoyMn1-x-y)1-aNbaO2MLBP lithium ion anode material, wherein m
For 0.02~5.
In certain embodiments, one or more of the described nickel salt in nickel nitrate, nickel acetate, nickel sulfate.
In certain embodiments, one or more of the described cobalt salt in cobalt nitrate, cobalt acetate, cobaltous sulfate.
In certain embodiments, one or more of the described manganese salt in manganese nitrate, manganese acetate, manganese sulfate.
In certain embodiments, described lithium salts is selected from the mixing of one or both of lithium hydroxide, lithium carbonate.
In certain embodiments, described Nb compound is one or two kinds of mixed in niobium oxide, niobium oxalate
Close.
In certain embodiments, lithium source can be lithium metaborate, lithium tetraborate and/or lithium hydroxide；Boron source can be boron
Acid, lithium metaborate and/or lithium tetraborate；Phosphorus source can be phosphoric acid and/or ammonium dihydrogen phosphate.
Embodiment 1
Prepare the Li (Ni for being coated with 2%LBP0.6Co0.2Mn0.2)0.95Nb0.05O2Positive electrode, it is comprised the following steps that：
(1) 4.081g lithium acetates, 5.674g nickel acetates, 1.893g cobalt acetates, 1.863g manganese acetates, 1.076g oxalic acid are weighed
Niobium, 2.620g citric acids and 5.012g ethylene glycol are all dissolved in 500ml deionized water, in the water that design temperature is 80 DEG C
Agitating and heating in bath, it is evaporated into after gel to be placed in 120 DEG C of baking ovens and dries 6h.Gel after drying is ground into loading crucible to put
In tube furnace, using air atmosphere, 850 DEG C of sintering 12h.The broken Nb that obtains of the material block grinding for sintering completion is adulterated into mole
For 0.05 622NCM materials.
(2) lithium metaborate, boric acid and ammonium dihydrogen phosphate are weighed according to LBP stoichiometric proportion, be dissolved in 90mL ethanol and
In the mixed liquor of 30mL water.The material that step (1) obtains is added while stirring, and the mass ratio for ensureing 622NCM and LBP is 98：2.
Mixed solution is positioned in 70 DEG C of water-bath, stirred, until liquid evaporation, tube furnace is placed in by obtained solid powder
In, in air atmosphere, 350 DEG C of calcining 5h, obtain final Nb doping and LBP coats the 622NCM positive pole materials of dual modification
Material.
Positive plate is made in the 622NCM positive electrodes for the dual modification that this experiment is obtained, and is then assembled into CR2032 buttons
Battery, test its chemical property.
Embodiment 2
Prepare the Li (Ni for being coated with 2%LBP0.6Co0.2Mn0.2)0.9Nb0.1O2Positive electrode, the present embodiment and embodiment 1
Unlike：The quality of each metal salt weighed in step (1) be respectively 4.081g lithium acetates, 5.375g nickel acetates,
1.793g cobalt acetates, 1.764g manganese acetates, 2.152g niobium oxalates.Other operating procedures and parameter are same as Example 1.
Embodiment 3
Prepare the Li (Ni for being coated with 1%LBP0.6Co0.2Mn0.2)0.95Nb0.05O2Positive electrode, the present embodiment and embodiment 1
Unlike：The mass ratio for ensureing 622NCM and LBP in step (2) is 99：1.Other operating procedures and parameter and the phase of embodiment 1
Together.
Embodiment 4
Prepare the Li (Ni for being coated with 2%LBP0.8Co0.1Mn0.1)0.95Nb0.05O2Positive electrode, the present embodiment and embodiment 1
Unlike：Weighed in step (1) 4.081g lithium acetates, 7.565g nickel acetates, 0.947g cobalt acetates, 0.931g manganese acetates,
1.076g niobium oxalates, 2.620g citric acids and 5.012g ethylene glycol are all dissolved in 500ml deionized water, in design temperature
For agitating and heating in 80 DEG C of water-baths, it is evaporated into after gel to be placed in 120 DEG C of baking ovens and dries 6h.Gel after drying is ground
It is fitted into crucible to be placed in tube furnace, using oxygen atmosphere, 780 DEG C of sintering 12h.The material block grinding for sintering completion is crushed and obtains Nb
Adulterate the 811NCM materials that mole is 0.05.Other operating procedures and parameter are same as Example 1.
Embodiment 5
The present embodiment is as different from Example 4：Using 100mL ethanol and the mixed solution of 20mL water in step (2).Its
His operating procedure and parameter are same as Example 4.
Embodiment 6
Prepare the Li (Ni for being coated with 2%LBP0.5Co0.2Mn0.3)0.95Nb0.05O2Positive electrode, comprise the following steps that：
(1) by lithium hydroxide, 523NCM presomas Ni0.5Co0.2Mn0.3(OH)2And niobium pentaoxide is in molar ratio
1.05：0.95：0.025 is well mixed, and the material mixed then is fitted into crucible and is placed in tube furnace, using air atmosphere,
900 DEG C of sintering 12h.The broken Nb that obtains of the material block grinding for sintering completion is adulterated into the 523NCM materials that mole is 0.05.
(2) lithium metaborate, boric acid and ammonium dihydrogen phosphate are weighed according to LBP stoichiometric proportion, be dissolved in 90mL ethanol and
In the mixed liquor of 30mL water.The material that step (1) obtains is added while stirring, and the mass ratio for ensureing 523NCM and LBP is 98：2.
Mixed solution is positioned in 80 DEG C of water-bath, stirred, until liquid evaporation, tube furnace is placed in by obtained solid powder
In, in air atmosphere, 350 DEG C of calcining 5h, obtain final Nb doping and LBP coats the 523NCM positive pole materials of dual modification
Material.
It is the three kinds of materials used in embodiment 2 as shown in Figure 1, under the conditions of room temperature, 2.8~4.3V, observes its 0.2C
First charge-discharge curve under multiplying power, it is seen then that charge-discharge performance is effectively improved.
The three kinds of materials used in embodiment 4 are illustrated in figure 5, under the conditions of room temperature, 2.8~4.3V, observe its 2C times
Cycle performance under rate, it is seen then that modified to effectively raise cyclical stability.
Positive plate is made in the 523NCM positive electrodes for the dual modification that this experiment is obtained, and is then assembled into CR2032 buttons
Battery, test its chemical property.
As shown in figure 3, Li (the Ni that pure 523NCM, Nb are adulterated0.5Co0.2Mn0.3)0.95Nb0.05O2(it is designated as 523NCM-
Nb0.05) and Nb doping coats the positive electrode (being designated as 523NCM-Nb0.05-2LBP) modified jointly with LBP and makees XRD.
It can draw, it is modified not occur new thing phase.
As shown in figure 4, each element in 523NCM-Nb0.05-2LBP materials is done into XPS collection of illustrative plates, it has P-O keys, Nb5+And
B presence.
As shown in figure 5, by used in Fig. 3 three kinds of materials, under the conditions of room temperature, 2.8~4.3V, observe its times it is forthright
Can, it is seen then that can effectively improve the high rate performance of battery.
Above-mentioned Fig. 3, Fig. 4, use in Fig. 5 is the material obtained in embodiment 6, and in other embodiment
The chemical property of material is more excellent, and it can effectively improve the high rate performance of positive electrode, improves cyclical stability.
Claims (10)
1. a kind of ion doping and Surface coating modify anode material for lithium-ion batteries jointly, it is characterised in that are that positive pole is lived
Property material use Nb ion dopings so that its formed particulate matter, and particulate matter surface use have quick conductive lithium from
The covering of sub- ability is coated on surface of positive electrode active material and formed.
2. ion doping as claimed in claim 1 and Surface coating modify anode material for lithium-ion batteries jointly, its feature exists
In described positive electrode active materials are nickel-cobalt lithium manganate materials.
3. ion doping as claimed in claim 2 and Surface coating modify anode material for lithium-ion batteries jointly, its feature exists
In described nickel-cobalt lithium manganate material is LiNi0.8Co0.1Mn0.1O2, LiNi0.6Co0.2Mn0.2O2, LiNi0.5Co0.2Mn0.3O2,
LiNi0.4Co0.2Mn0.4O2, LiNi1/3Co1/3Mn1/3O2In one kind.
4. ion doping as claimed in claim 2 or claim 3 and Surface coating modify anode material for lithium-ion batteries jointly, its feature
It is, described nickel-cobalt lithium manganate material is spheric granules, spherical particle, bar-shaped or sheet.
5. ion doping as claimed in claim 1 and Surface coating modify anode material for lithium-ion batteries jointly, its feature exists
In described covering 0.035Li2O·BPO4。
6. ion doping as claimed in claim 1 and Surface coating modify anode material for lithium-ion batteries jointly, its feature exists
In described covering cladding is by the positive electrode active materials top layer of Nb ion dopings by covering by growth in situ.
7. ion doping as claimed in claim 1 and Surface coating modify anode material for lithium-ion batteries jointly, its feature exists
In described uses Nb ion dopings, and metallic element Nb molar content is 0.005~0.2% after doping.
8. the ion doping and Surface coating as described in claim 1 or 5 or 6 modify anode material for lithium-ion batteries jointly, its
It is characterised by, described covering, after cladding, accounts for the 0.02~5% of anode material for lithium-ion batteries gross mass.
9. the ion doping and Surface coating as described in claim 1 or 6 modify anode material for lithium-ion batteries jointly, its feature
It is, described covering cladding, thickness is 5~50nm.
10. the ion doping and Surface coating as described in claim any one of 1-9 modify anode material for lithium-ion batteries jointly
Preparation method, it is characterised in that comprise the following steps：
(1) according to positive electrode active materials formula Li (NixCoyMn1-x-y)1-aNbaO2In stoichiometric proportion, weigh nickel salt, cobalt salt,
Manganese salt, lithium salts, Nb compound, are added in deionized water, and with 500mL deionized waters add 2.620g citric acids and
Colloidal sol is made in 5.012g ethylene glycol, dissolving, is evaporated as gel, dries, is placed in sintering furnace, is calcined at 750-1000 DEG C
6-15h, crush, grinding, obtain Li (NixCoyMn1-x-y)1-aNbaO2Material, wherein, a is 0.005~0.2；Or according to positive pole
Active material formula Li (NixCoyMn1-x-y)1-aNbaO2In stoichiometric proportion, weigh nickel salt, cobalt salt, manganese salt, lithium salts, Nb
Compound, it is sufficiently mixed uniformly, after the completion of mixing, is placed in sintering furnace, 6-15h is calcined at 750-1000 DEG C, crushes, grind
Mill, obtains Li (NixCoyMn1-x-y)1-aNbaO2Material, wherein, a is 0.005~0.2；
(2) it is 0.035Li according to chemical formula2O·BPO4Molar ratio weighing lithium source, phosphorus source, the boron source of middle each element, and be dissolved in
Second alcohol and water is 0~7 according to volume ratio:In 1 mixed liquor mixed, LBP is obtained；The Li that step (1) is obtained again
(NixCoyMn1-x-y)1-aNbaO2Material is added thereto, and stirring, heating evaporation, is obtained solid powder, is placed in calcining furnace, 250
2-6h is calcined at~600 DEG C, obtains (1-m) Li (NixCoyMn1-x-y)1-aNbaO2MLBP lithium ion anode material, wherein m
For 0.02~5.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108390045A (en) * | 2018-03-09 | 2018-08-10 | 长沙理工大学 | A kind of netted superionic glass conductor coats transient metal doped ternary cathode material of lithium ion battery and preparation method |
| CN109119611A (en) * | 2018-08-22 | 2019-01-01 | 广东工业大学 | A kind of method that one-step method realizes ion doping and the common modification tertiary cathode material of surface cladding |
| CN110148744A (en) * | 2019-05-30 | 2019-08-20 | 桑顿新能源科技(长沙)有限公司 | Modified nickle cobalt lithium manganate NCM111 tertiary cathode material and preparation method thereof and battery |
| CN110247035A (en) * | 2019-06-06 | 2019-09-17 | 山东省科学院能源研究所 | A kind of nickelic positive electrode method of modifying |
| CN110931733A (en) * | 2019-11-13 | 2020-03-27 | 北京理工大学 | Surface manganese doping and Li-Mn-PO4Coated high-nickel positive electrode material and preparation method and application thereof |
| CN111029535A (en) * | 2018-10-09 | 2020-04-17 | 北大先行科技产业有限公司 | Composite positive electrode material of lithium ion battery and preparation method thereof |
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2017
- 2017-10-17 CN CN201710964287.3A patent/CN107768634A/en active Pending
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| WUJIE GE等: ""Amorphous 0.035Li2O-BPO4 coating for enhanced electrochemical performance of Li[Ni0.5Co0.2Mn0.3]O2 cathode material"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108390045A (en) * | 2018-03-09 | 2018-08-10 | 长沙理工大学 | A kind of netted superionic glass conductor coats transient metal doped ternary cathode material of lithium ion battery and preparation method |
| CN109119611A (en) * | 2018-08-22 | 2019-01-01 | 广东工业大学 | A kind of method that one-step method realizes ion doping and the common modification tertiary cathode material of surface cladding |
| CN111029535A (en) * | 2018-10-09 | 2020-04-17 | 北大先行科技产业有限公司 | Composite positive electrode material of lithium ion battery and preparation method thereof |
| CN110148744A (en) * | 2019-05-30 | 2019-08-20 | 桑顿新能源科技(长沙)有限公司 | Modified nickle cobalt lithium manganate NCM111 tertiary cathode material and preparation method thereof and battery |
| CN110148744B (en) * | 2019-05-30 | 2022-06-14 | 桑顿新能源科技(长沙)有限公司 | Modified nickel cobalt lithium manganate NCM111 ternary cathode material, preparation method thereof and battery |
| CN110247035A (en) * | 2019-06-06 | 2019-09-17 | 山东省科学院能源研究所 | A kind of nickelic positive electrode method of modifying |
| CN110931733A (en) * | 2019-11-13 | 2020-03-27 | 北京理工大学 | Surface manganese doping and Li-Mn-PO4Coated high-nickel positive electrode material and preparation method and application thereof |
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Application publication date: 20180306 |