CN107834061A - A kind of method of modifying for improving lithium-rich manganese base material chemical property - Google Patents
A kind of method of modifying for improving lithium-rich manganese base material chemical property Download PDFInfo
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- CN107834061A CN107834061A CN201711144284.1A CN201711144284A CN107834061A CN 107834061 A CN107834061 A CN 107834061A CN 201711144284 A CN201711144284 A CN 201711144284A CN 107834061 A CN107834061 A CN 107834061A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention provides a kind of method of modifying for improving lithium-rich manganese base material chemical property, it is characterized in that, three-dimensional conductive network in the active substances in cathode materials of the lithium-rich manganese base material is by two-dimentional conductive agent graphene, one or more in CNT, carbon fiber, one or more in one-dimensional electric agent and SP conductive agents, acetylene black, electrically conductive graphite, zero dimension conductive agent are combined.The lithium-rich manganese base material positive plate with comprehensive three-dimensional conductive network prepared using the present invention, compared to traditional pole piece, with higher electronic conductivity and lithium ion diffusion rate, the combination of active material and collector is more close simultaneously, the polarity effect of welfare Mn-based material battery can be greatly reduced, battery high rate performance is significantly improved, while can also improve the cyclical stability of battery.Step is simple and convenient to operate, is practical.
Description
Technical field
The invention belongs to lithium battery material field, and in particular to a kind of method of lithium ion battery lithium-rich manganese base
And modified technique.
Background technology
Lithium-ion-power cell has big operating voltage height, energy density, in light weight, small volume, self-discharge rate is small, circulates
Long lifespan, memory-less effect, have a safety feature, anti-bulging excellent performance, it is environmentally friendly the features such as, turn into electric car and mixed
Close the main vehicle mounted dynamic battery of the new energy cars such as power car.At present, electric automobile mainly faces that course continuation mileage is short and security
The problems such as insufficient, the deficiency of electrokinetic cell performance constrain its large-scale promotion.Recently, the Ministry of Science and Technology, Ministry of Industry and Information etc. are relevant
Department represents that the year two thousand twenty electrokinetic cell energy density monomer must reach 300Wh/kg, and further object is 350Wh/kg.
And the performance of lithium ion battery depends primarily on the performance of positive and negative electrode material, therefore, high performance positive electrode is researched and developed for promoting
The development for entering new-energy automobile is significant.
The positive electrode of power train in vehicle application type lithium battery mainly has LiFePO4, LiMn2O4, low nickel ternary material (NCM) at present
Deng the Common advantages of these positive electrodes are that security performance and stability are preferable, but monomer energy density is generally relatively low, typically
Above and below 150Wh/kg.Height ratio capacity positive electrode NCM811 and nickel cobalt aluminium (NCA) are although coordinate silicon-carbon cathode to make battery
Monomer energy density reaches 300Wh/kg, but is unable to reach 350Wh/kg, and NCM811 security performance and stable circulation
Sex chromosome mosaicism is not yet resolved；The technical threshold of NCA batteries is high, and the only fewer companies such as PANASONIC are grasped at present.Known
In positive electrode, lithium-rich manganese-based anode material Li2MnO3·LiMO2(M=Ni, Co, Mn ...) has that cost is low, non-toxic and safe, put
The advantages that electric specific capacity is up to 250-300mAh/g, it is that Current commercialization is put using positive electrodes such as LiFePO4 and ternary materials
Twice or so of electric specific capacity, thus it is considered as the choosing of the ideal of high-energy-density dynamic lithium battery positive electrode of new generation, energy
Enough meet requirement of the lithium battery in fields such as electric automobiles.But the Li in lithium-rich manganese base material2MnO3Phase component has pole
Low electrical conductivity and ion diffusion rates, and lithium-rich manganese base material is easy to electrolyte and the thick SEI layers of side reaction generation occurs, no
Beneficial to electronics and lithium ion transport, therefore the high rate performance of rich lithium material is poor.
The pertinent literature and patent for improving lithium-rich manganese base material high rate performance mainly have：Element doping, Surface coating and
Conductive agent from excellent electric conductivity etc..Such as：It is lithium-rich manganese-based just that Publication No. CN106654251A patent discloses one kind
Pole material modification method, by using Li with lithium2CO3And Li2RuO3Compound lithium salts introduces Ru ions, alleviate Mn ion pairs lithium from
The obstruction of sub- diffusion admittance, help improve the high rate performance of material.And for example 104681809A patent discloses a kind of rich lithium manganese
The method of modifying of base anode material：By presoma, lithium carbonate, the full and uniform mixing of doping vario-property chloric metal-salt, then carry out high
Temperature sintering obtains modified lithium-rich manganese-based anode material, and this method can be in complete machine table by optimizing metal salt species and sintering schedule
Face forms LiAlO2、Li2ZrO3、Li2TiO3Deng lithium ion clad, effectively alleviate corruption of the electrolyte to active substances in cathode materials
The formation of the suppression SEI films of erosion, while quick transmission channel is provided for the deintercalation process of lithium ion, contribute to the material circulation life-span
With the raising of high rate performance.
In fact, at the beginning of lithium ion battery is born certainly, dependence just is generated to conductive agent material.From earliest carbon black material
Material, such as the zero dimension conductive agent such as AB, SP, to the newest laminar structured grapheme two-dimension material with two dimension, all it is added into
To strengthen the electric conductivity of positive electrode in lithium battery, the performance of battery is improved.But prior art is to the composition research of conductive agent
It is less, often through high-performance conductive agent simple superposition or replace to realize performance upgrade, such as：Publication number CN102544575A
Patent its only describe positive conductive agent as conductive black, superconduction carbon, electrically conductive graphite, crystalline flake graphite, one in CNT
Kind is several.But this mode is clearly poorly efficient and worthless.
The content of the invention
It is of the invention by building a kind of comprehensive three-dimensional conductive network in positive electrode in order to overcome above-mentioned deficiency, from
And the electric conductivity of lithium-rich manganese-based anode material is improved, and then improve the chemical properties such as its high rate performance.Described comprehensive three
Dimension conductive network is interweaved by the three-dimensional conductive network and the conductive network of collection liquid surface that are distributed among active material to be formed.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of method of modifying for improving lithium-rich manganese base material chemical property, the positive electrode of the lithium-rich manganese base material are lived
Property material has three-dimensional conductive network, and the three-dimensional conductive network is by two-dimentional conductive agent and/or one-dimensional electric agent, zero dimension conductive agent
It is combined；
In order to improve existing lithium battery conductive material utilization ratio, the present invention advises to the compounding of existing conductive agent material
Rule has made intensive studies, and finds：Using two-dimentional conductive agent graphene and/or one-dimensional electric agent CNT and zero dimension conductive agent
When compounding, three-dimensional conductive network can be formed, and produce synergetic；While improving electric conductivity, effectively reduce
Cost of material.
Preferably, the three-dimensional conductive network content in the active substances in cathode materials by weight percent for 2%~
20%.
Preferably, binding agent is the group of butadiene-styrene rubber (SBR) and sodium carboxymethylcellulose (CMC) in the positive electrode
Close, gather inclined fluorine vinyl chloride (PVDF), polytetrafluoroethylene (PTFE) (PTFE) or poly- inclined fluorine vinyl chloride-hexafluoropropene (PVDF-HFP), it is described
Mass percent of the binding agent in positive electrode is 3%~10%.
Present invention also offers a kind of lithium ion battery lithium-rich manganese base with comprehensive three-dimensional conductive network
Preparation method, including：
1) a certain amount of two-dimentional conductive agent and/or one-dimensional electric agent, lithium-rich manganese base material are disperseed in a solvent respectively equal
It is even, obtain conductive agent solution and lithium-rich manganese base material solution；
2) above-mentioned conductive agent solution is added dropwise in lithium-rich manganese base material solution, is well mixed, obtains slurry, dried, i.e.,
There must be the active substances in cathode materials of three-dimensional conductive network；
3) the above-mentioned active substances in cathode materials with three-dimensional conductive network is sufficiently mixed with zero dimension conductive agent, points 5~
It is added in the 1-METHYLPYRROLIDONE dissolved with binding agent (NMP) solution for 10 times, per 1~2h of minor tick, is well mixed, produces
Lithium-rich manganese-based anode material slurry.
Preferably, the lithium-rich manganese base material is micron-size spherical second particle or nano particle.
Preferably, the solvent is including but not limited to water, ethanol, one kind in acetone.
Preferably, the process for dispersing is 5~60min of ultrasonic disperse.
Preferably, in step 2), well mixed method is：4~12h is continuously stirred at 40~80 DEG C.
Preferably, the drying is carried out at 80-120 DEG C.
Present invention also offers a kind of lithium ion battery lithium-rich manganese base material positive pole with comprehensive three-dimensional conductive network
Preparation method, including：
1) collection liquid surface conductive network is prepared, a certain amount of conductive agent and binding agent are dissolved in NMP and stirred,
Uniformly it is coated on aluminium foil, obtains the collector with conductive network；
2) above-mentioned lithium-rich manganese-based anode material slurry is uniformly coated to above-mentioned collector, baking, had
The lithium-rich manganese-based anode pole piece of comprehensive three-dimensional conductive network.
Preferably, the collector is aluminium foil.
Preferably, in step 1), the condition of baking is：60~90 DEG C of 20~60min of baking.
The lithium ion battery with comprehensive three-dimensional conductive network prepared present invention also offers any above-mentioned method is rich
Lithium Mn-based material positive pole.
Present invention also offers application of the three-dimensional conductive network in battery high rate performance and cyclical stability is improved, its
In, the three-dimensional conductive network is combined by two-dimentional conductive agent and/or one-dimensional electric agent, zero dimension conductive agent.
Beneficial effects of the present invention
(1) the lithium-rich manganese base material positive plate with comprehensive three-dimensional conductive network prepared using the present invention, compared to biography
System pole piece, has higher electronic conductivity and lithium ion diffusion rate, while the combination of active material and collector is more tight
It is close, the polarity effect of welfare Mn-based material battery can be greatly reduced, significantly improve battery high rate performance, while can also improve battery
Cyclical stability.
(2) preparation method of the present invention is simple, efficiency high, practical, easy to spread.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
The present invention in positive electrode by building a kind of comprehensive three-dimensional conductive network, so as to improve lithium-rich manganese-based anode
The electric conductivity of material, and then improve the chemical properties such as its high rate performance.The comprehensive three-dimensional conductive network is by being distributed in
The conductive network of three-dimensional conductive network and collection liquid surface among active material, which interweaves, to be formed.
Preferably, the collector is aluminium foil.
Preferably, the three-dimensional conductive network in the active substances in cathode materials is received by two-dimentional conductive agent graphene, carbon
One or more of one-dimensional electric agent in mitron, carbon fiber, and the one or more in SP conductive agents, acetylene black, electrically conductive graphite
Zero dimension conductive agent is combined.
Preferably, three-dimensional conductive network content in the active substances in cathode materials by weight percent for 2%~
20%.
Preferably, in the positive electrode binding agent be SBR combined with CMC, one in PVDF, PTFE, PVDF-HFP
Kind, mass percent is 3%~10%.
Preferably, the collection liquid surface conductive network is by graphene, CNT, carbon fiber, SP conductive agents, acetylene
One or more in black and electrically conductive graphite are combined.
Preferably, collection liquid surface conductive coating thickness is 100nm~100 μm.
Meanwhile the present invention provides the above-mentioned lithium ion battery lithium-rich manganese base material positive pole with comprehensive three-dimensional conductive network
Preparation method, including：Three-dimensional conductive network and collector conductive network prepare two parts between active substances in cathode materials, including with
Lower step：
Step 1：The preparation of three-dimensional conductive network between active substances in cathode materials, preferably, there is two methods：
First method：
(1) by it is above-mentioned will be one or more of and lithium-rich manganese-based in a certain amount of graphene, CNT, carbon fibre material
Material is scattered in solvent respectively, and 5~60min of ultrasonic disperse；
(2) conductive agent solution will be obtained to be added dropwise in lithium-rich manganese base material solution, and 4 is continuously stirred at 40~80 DEG C
~12h, obtain the slurry of thickness.
(3) gained slurry is dried at 80-120 DEG C, obtains the active substances in cathode materials with three-dimensional conductive network；
(4) quantitative binding agent is dissolved in NMP, then filled active material resulting in step (3) with zero dimension conductive agent
Point mixing, is added in nmp solution points for 5~10 times, per 1~2h of minor tick, is subsequently placed in agitator, it is sufficiently stirred 4~
20h, obtain uniform lithium-rich manganese-based anode material slurry.
Preferably, the lithium-rich manganese base material in (1) can be micron-size spherical second particle or nanometer
Grain.
Preferably, solvent in (1) is including but not limited to water, ethanol, one kind in acetone.
Second method：
Step 1：Binding agent is dissolved in NMP, by lithium-rich manganese-based active material, two dimension and/or one-dimensional electric agent, zero dimension
After conductive agent is sufficiently mixed, divides 5~10 times and be added in nmp solution, per 1~2h of minor tick, be sufficiently stirred 6~20h and obtain
Even lithium-rich manganese base material slurry.
Step 2：Prepare collection liquid surface conductive network.A certain amount of conductive agent and binding agent are dissolved in NMP and stirred
Uniformly, uniformly it is coated on aluminium foil, toasts 20~60min at 60~90 DEG C, obtain the collector with conductive network.
Step 3：By the slurry prepared in step 1 uniformly on coating to the collector, and dry, obtain having comprehensively
The lithium-rich manganese-based anode pole piece of three-dimensional conductive network.
Further preferably, it is not susceptible to graphene and CNT/carbon fiber in slurry obtained by the first method
Stack and reunite, and disperse to be more uniformly distributed with active material.Coat in the positive plate obtained to collector, conductive network more adds
It is whole.Better than slurry obtained by second method.
The above-mentioned lithium-rich manganese base material pole piece with comprehensive three-dimensional conductive network is prepared and its in lithium ion battery
Using the protection domain for being also the invention.
The present invention improves the Modification design thinking of lithium-rich manganese base material high rate performance：
1) built between rich lithium material active material by graphene, CNT, carbon fiber and Super P, acetylene black etc.
Zero dimension leads the three-dimensional conductive network that conductive agent intertexture is combined, and this composite conducting network can give full play to graphene conductive
Rate is high, and specific surface area is big, can be with active material bump contact；CNT and electric conduction of carbon fiber rate are high, and draw ratio is big, easily
In formation conductive network；The zero dimension material granule such as Super P is small, can with filling pore etc. it is respective the advantages of, and produce collaboration effect
Should.It is special when conductive agent is graphene, CNT and Super P/ acetylene black three's compound tenses, it is complete structure can be built
Whole, intensity is high, and contact area is big, and conductance is high, while improves lithium ion diffusion rate and the three-dimensional conductive of electron transfer rate
Network.The maximum relative electrical conductivity and lithium ion diffusion rate for lifting rich lithium material of energy, so as to improve high rate performance.
2) impedance between active material and collector on the one hand can be reduced in collection liquid surface structure conductive network, separately
On the one hand the adhesion between active material and collector can be improved, so as to improve chemical property.The present invention uses first
Simple conductive agent nmp solution slurry coating is prepared into conductive network, and when being coated with active material slurry, the NMP in slurry can
So that the superficial layer of underlying conductive network to be dissolved again, enable positive electrode slurry and lower floor's collection liquid surface conductive network phase
Counterdiffusion and immersion, allow the mutual weave in of the conductive agent in the two, can reduce to a greater extent therebetween
Impedance, improve bond strength therebetween.
Embodiment 1：A kind of modified preparation for lifting lithium-rich manganese base material high rate performance
The anode pole piece includes：Collector, conductive network on a current collector is coated, and there is three-dimensional conductive network
Active material.
The collector is general commercial aluminium foil；
The collection liquid surface conductive network is made up of 1 part of PVDF and 20 part of graphene；
The active material coating is by 75 parts of lithium-rich manganese base material Li1.2Mn0.54Ni0.13Co0.13O2, 2.5 parts of graphenes,
2.5 parts of CNTs, 10 parts of SP, 10 parts of PVDF compositions.
Preparation method is as follows：
(1) load weighted graphene, CNT and lithium-rich manganese base material are scattered in ethanol respectively, and ultrasonic disperse
30min；
(2) graphene solution is added dropwise in carbon nano-tube solution, is ultrasonically treated 30min；
(3) above-mentioned composite conducting agent solution is added dropwise in lithium-rich manganese base material solution, and it is continuous at 40~80 DEG C
12h is stirred, obtains the slurry of thickness.
(4) gained slurry is dried at 80 DEG C, obtains the active substances in cathode materials with three-dimensional conductive network；
(5) load weighted binding agent is dissolved in NMP, then filled active substances in cathode materials resulting in (4) with SP
Divide mixing, divide 5 times and be added in nmp solution, per minor tick 1h, be subsequently placed in agitator, be sufficiently stirred 10h and obtain uniformly
Lithium-rich manganese-based anode material slurry.
(6) quantitative binding agent is dissolved in NMP, quantitative graphite alkene is then scattered in ultrasonic disperse 30min in NMP, afterwards
1h is stirred, is coated to aluminium foil, 30min is toasted at 80 DEG C, coating layer thickness is 1 μm.
(7) lithium-rich manganese-based anode material slurry prepared by step (5) is coated on the collector prepared to step (6), and
2h are toasted at 80 DEG C, afterwards 120 DEG C of vacuum bakeout 12h again.Coating thickness is 30 μm.
Embodiment 2
The anode pole piece includes：Collector, conductive network on a current collector is coated, and there is three-dimensional conductive network
Active material.
The collector is general commercial aluminium foil；
The collection liquid surface conductive network is made up of 1 part of PVDF and 20 part of graphene；
The active material coating is by 75 parts of lithium-rich manganese base material Li1.2Mn0.54Ni0.13Co0.13O2, 5 parts of graphenes, 10 parts
SP, 10 parts of PVDF compositions.
Preparation method is same as Example 1.
Embodiment 3
The anode pole piece includes：Collector, conductive network on a current collector is coated, and there is three-dimensional conductive network
Active material.
The collector is general commercial aluminium foil；
The collection liquid surface conductive network is made up of 1 part of PVDF and 20 part of graphene；
The active material coating is by 75 parts of lithium-rich manganese base material Li1.2Mn0.54Ni0.13Co0.13O2, 5 parts of CNTs, 10
Part SP, 10 parts of PVDF compositions.
Preparation method is same as Example 1.
Comparative example 1：
The anode pole piece includes：Collector, active material.
The collector is general commercial aluminium foil；
The active material coating is by 75 parts of lithium-rich manganese base material Li1.2Mn0.54Ni0.13Co0.13O2, 15 parts of SP, 10 parts
PVDF is formed.
(1) quantitative binding agent is dissolved in NMP, be then sufficiently mixed active material and SP, divided 5 times and be added to nmp solution
In, per minor tick 1h, it is subsequently placed in agitator, is sufficiently stirred 10h and obtains uniform lithium-rich manganese base material slurry.
(2) lithium-rich manganese base material slurry is coated to collector, and 2h is toasted at 80 DEG C, 120 DEG C of vacuum are dried again afterwards
Roasting 12h.Coating thickness is 30 μm of
Comparative example 2
The anode pole piece includes：Collector, coat conductive network on a current collector, and active material.
The collector is general commercial aluminium foil；
The collection liquid surface conductive network is made up of 1 part of PVDF and 20 part of graphene；
The active material coating is by 75 parts of lithium-rich manganese base material Li1.2Mn0.54Ni0.13Co0.13O2, 15 parts of SP, 10 parts
PVDF is formed.
Preparation method is same as Example 1.
Comparative example 3
The anode pole piece includes：Collector, and active material.
The collection liquid surface conductive network is made up of 1 part of PVDF and 20 part of graphene；
The active material coating is by 75 parts of lithium-rich manganese base material Li1.2Mn0.54Ni0.13Co0.13O2, 15 parts of graphenes, 10
Part PVDF compositions.
Preparation method is same as Example 1.
Comparative example 4
The anode pole piece includes：Collector, coat conductive network on a current collector, and active material.
The collection liquid surface conductive network is made up of 1 part of PVDF and 20 part of graphene；
The active material coating is by 75 parts of lithium-rich manganese base material Li1.2Mn0.54Ni0.13Co0.13O2, 15 parts of graphenes, 10
Part PVDF compositions.
Preparation method is same as Example 1.
Respectively with embodiment 1,2,3 and comparative example 1, the positive plate prepared by 2,3,4 is positive pole, and lithium piece is prepared into for negative pole
2032 types buckle electricity, two battery multiplying powers and cycle performance are tested using blue electric system, test result is as shown in table 1.
Table 1
Finally it should be noted that the foregoing is only the preferred embodiments of the present invention, this hair is not limited to
Bright, although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it is still
Technical scheme described in previous embodiment can be modified, or equivalent substitution is carried out to which part.It is all in this hair
Within bright spirit and principle, any modification, equivalent substitution and improvements made etc., protection scope of the present invention should be included in
Within.Although the above-mentioned embodiment to the present invention is described, not limiting the scope of the invention, institute
Category art personnel should be understood that on the basis of technical scheme those skilled in the art need not pay wound
The various modifications or deformation that the property made work can be made are still within protection scope of the present invention.
Claims (10)
1. a kind of method of modifying for improving lithium-rich manganese base material chemical property, it is characterised in that the lithium-rich manganese base material
Active substances in cathode materials has a three-dimensional conductive network, the three-dimensional conductive network by two-dimentional conductive agent and/or one-dimensional electric agent,
Zero dimension conductive agent is combined.
2. the method as described in claim 1, it is characterised in that the two-dimentional conductive agent is graphene or class graphene carbon materials
Material, the one-dimensional electric agent are CNT or carbon fiber, and the zero dimension conductive agent is carbon black SP, acetylene black or electrically conductive graphite.
3. the method as described in claim 1, it is characterised in that the three-dimensional conductive network in the active substances in cathode materials contains
Amount is 2%~20% by weight percent.
4. the method as described in claim 1, it is characterised in that binding agent is styrene butadiene rubber sbr and carboxylic in the positive electrode
Sodium carboxymethylcellulose pyce CMC's combines, gathers inclined fluorine vinyl chloride PVDF, polytetrafluoroethylene PTFE or gather inclined fluorine vinyl chloride-hexafluoropropene
PVDF-HFP, mass percent of the binding agent in positive electrode are 3%~10%.
5. a kind of preparation method of the lithium ion battery lithium-rich manganese base with comprehensive three-dimensional conductive network, including：
1) a certain amount of two-dimentional conductive agent and/or one-dimensional electric agent, lithium-rich manganese base material are uniformly dispersed in a solvent respectively, obtained
Conductive agent solution and lithium-rich manganese base material solution；
2) above-mentioned conductive agent solution is added dropwise in lithium-rich manganese base material solution, is well mixed, obtains slurry, dried, produce tool
There is the active substances in cathode materials of three-dimensional conductive network；
3) the above-mentioned active substances in cathode materials with three-dimensional conductive network is sufficiently mixed with zero dimension conductive agent, divided 5~10 times
It is added in the 1-METHYLPYRROLIDONE nmp solution dissolved with binding agent, per 1~2h of minor tick, is well mixed, produces rich lithium manganese
Base anode material slurry.
6. method as claimed in claim 5, it is characterised in that the lithium-rich manganese base material be micron-size spherical second particle or
Nano particle.
7. a kind of preparation method of the lithium ion battery lithium-rich manganese base material positive pole with comprehensive three-dimensional conductive network, including：
1) collection liquid surface conductive network is prepared, a certain amount of conductive agent and binding agent are dissolved in NMP and stirred, uniformly
It is coated on aluminium foil, toasts, obtain the collector with conductive network；
2) the lithium-rich manganese-based anode material slurry described in claim 5 or 6 is uniformly coated to above-mentioned collector, baking,
Obtain the lithium-rich manganese-based anode pole piece with comprehensive three-dimensional conductive network.
8. method as claimed in claim 7, it is characterised in that the collector is aluminium foil.
9. lithium-rich manganese base material positive pole prepared by the method described in claim any one of 1-8.
10. application of the three-dimensional conductive network in battery high rate performance and cyclical stability is improved, it is characterised in that the three-dimensional
Conductive network is combined by two-dimentional conductive agent and/or one-dimensional electric agent, zero dimension conductive agent.
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| CN114388274A (en) * | 2021-12-30 | 2022-04-22 | 浙江浙能中科储能科技有限公司 | Ion and electron composite conduction electrode and in-situ preparation method thereof |
| CN114388274B (en) * | 2021-12-30 | 2024-02-02 | 浙江浙能中科储能科技有限公司 | Ion and electron composite conducting electrode and in-situ preparation method thereof |
| CN115084521A (en) * | 2022-06-17 | 2022-09-20 | 贵州旌麾科技有限公司 | Multi-element composite conductive agent for metal lithium battery and preparation method and application thereof |
| CN115548246A (en) * | 2022-08-30 | 2022-12-30 | 哈尔滨工程大学 | Preparation method of lithium thionyl chloride battery positive electrode reaction carrier material |
| CN115411250A (en) * | 2022-09-15 | 2022-11-29 | 山东大学 | Preparation method and application of modified lithium-rich manganese-based positive electrode of lithium ion battery |
| CN116581280A (en) * | 2023-07-12 | 2023-08-11 | 深圳海辰储能控制技术有限公司 | Positive electrode material, preparation method thereof, positive electrode plate and lithium battery |
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