CN107403933A - A kind of lithium ion battery electrode piece and preparation method thereof and application - Google Patents

A kind of lithium ion battery electrode piece and preparation method thereof and application Download PDF

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Publication number
CN107403933A
CN107403933A CN201710554731.4A CN201710554731A CN107403933A CN 107403933 A CN107403933 A CN 107403933A CN 201710554731 A CN201710554731 A CN 201710554731A CN 107403933 A CN107403933 A CN 107403933A
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ion battery
lithium ion
battery electrode
electrode piece
active material
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陈永胜
黄晓艳
随东
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Tianjin Plannano Technology Co Ltd
Tianjin Pulan Nano Technology Co Ltd
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Tianjin Plannano Technology Co Ltd
Tianjin Pulan Nano Technology Co Ltd
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Priority to CN201710554731.4A priority Critical patent/CN107403933A/en
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
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    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of lithium ion battery electrode piece and preparation method thereof and application, electrode plates include binding agent, conductive agent, active material and collector, can be on the premise of the rigid structure of pole piece be ensured using polytetrafluoroethylene (PTFE) as binding agent, suppress its volumetric expansion, solvent is no longer added to make slurry, simplify technological process, improve compacted density, and pole piece thickness and load capacity is caused to become more controllable, and then improve the performance of lithium ion battery, and the electrode slice that this programme is related to is applicable not only to the negative material with volumetric expansion, it can equally be well applied to other various positive and negative pole materials.

Description

A kind of lithium ion battery electrode piece and preparation method thereof and application
Technical field
The invention belongs to technical field of lithium ion, more particularly, to a kind of lithium ion battery electrode piece and its making Methods and applications.
Background technology
Lithium ion battery has the advantages that energy density high, good cycle and cost-effective, is widely used at present In portable type electronic product, and it is expected to turn into the energy resource supply of hybrid vehicle and power vehicle.Commercial Li-ion at present Battery is mainly using carbonaceous materials such as graphite, but its theoretical capacity only has 372mAh/g, can not meet high-energy positive electrode Requirement, therefore researcher have found the new silica-base material with up to 4200mAh/g specific capacities, but this material is de- Serious volumetric expansion in process of intercalation be present, to its capacity rapid decay.
In order to overcome disadvantage mentioned above, researchers from regulation activity material microstructure, from the side such as suitable binding agent Start with face.For binding agent, patent CN204257752U discloses a kind of lithium ion battery negative electrode plate, and the electrode slice is by silicon Carbon complex microsphere and Kynoar (PVDF) film are formed, and improve infringement of the volumetric expansion contraction to battery in charge and discharge process Problem, while addition conductive black is not required in homogenization process, simplify homogenate technique.Patent CN104953124A discloses one The binding agent of kind silicon-carbon cathode material, cathode pole piece of silicon-carbon battery and preparation method thereof, silicon-carbon battery, silicon-carbon cathode material Binding agent includes the polymer of hydroxyl and the polymer containing carboxyl, is dehydrated to form ester group at high temperature using carboxyl and hydroxyl Characteristic, the binding agent in pole piece is cross-linked into network structure, there is good rigid structure, it is suppressed that the change of pole piece thickness Change.Although pole piece preparation method inhibits the change of pole piece thickness to a certain extent used in above patent, it is in life Substantial amounts of solvent has been used to make slurry during production, if active material particle heterogeneity, in slurry coating procedure Easily there is cut, so as to influence the chemical property of electrode material, and it is coated after need to remove solvent, technique is cumbersome, together When also increase pole piece thickness and the uncontrollable factor of load capacity.
The content of the invention
In order to solve the above technical problems, the present invention provides a kind of lithium ion battery electrode piece and preparation method thereof and should With having selected a kind of novel binders, obtained electrode slice is applicable not only to the negative material with volumetric expansion, equally also fitted For other positive and negative pole materials.
The technical solution adopted by the present invention is：A kind of lithium ion battery electrode piece film, by binding agent and active material system Into wherein binding agent mass fraction is 1-20, and active material mass fraction is 60-99.
Preferably, bonding agent is polytetrafluoroethylene (PTFE).
Preferably, in addition to conductive agent, the conductive agent mass fraction are no more than 20.
Preferably, conductive agent is Super P-Li, acetylene black, graphite, KS-6, carbon ball, CNT, carbon fiber, activity One or more of combinations in charcoal.
Preferably, active material is electrode material；
Preferably, the electrode material is cobalt acid lithium, spinel lithium manganate, spinel nickel LiMn2O4, multicomponent material, metatitanic acid One kind in lithium, graphite, nano silicon material, silicon carbon material, LiFePO4, lithium ferric manganese phosphate, lithium vanadate.
Preferably, multicomponent material LiNixCoyMnzO2, wherein 0≤x≤1,0≤y≤1,0≤z≤1.
Lithium ion battery electrode piece made of a kind of lithium ion battery electrode piece film, by the lithium ion cell electrode Pole piece film coats on a current collector.
Preferably, collector is one kind in copper foil, netted copper foil, aluminium foil, netted aluminium foil, utter misery copper foil, utter misery aluminium foil.
A kind of method for preparing lithium ion battery electrode piece film, preparation process are as follows：
The active material that step 1 takes mass fraction to be 1-20 is ground into uniform powder；
Step 2 adds the binding agent that mass fraction is 60-99 into powder, again by rolling after being sufficiently mixed uniformly To uniform and smooth smooth film；
Preferably, the conductive agent that mass fraction is no more than 20 is added into the active material of step 1, is well mixed grinding Into powder；
Preferably, gained film thickness is 5-1000 μm in step 2.
A kind of method for preparing lithium ion battery electrode piece, preparation process are as follows：
The active material that step 1 takes mass fraction to be 1-20 is ground into uniform powder；
Step 2 adds the binding agent that mass fraction is 60-99 into powder, again by rolling after being sufficiently mixed uniformly To uniform and smooth smooth film；
The film is hot-pressed onto on the collector by step 3, and lithium ion battery electrode piece is made.
Preferably, the conductive agent that mass fraction is no more than 20 is added into the active material of step 1, is well mixed grinding Into powder；
Preferably, gained film thickness is 5-1000 μm in step 2.
Preferably, hot pressing pressure is 0.1-20MPa in step 3.
Preferably, hot pressing temperature is 20-300 DEG C in step 3.
Application of the lithium ion battery electrode piece in lithium battery positive and negative pole material, for there is the negative pole material of volumetric expansion Material.
The present invention has the advantages and positive effects of：This programme has selected a kind of novel binders, and polytetrafluoroethylene (PTFE) can Film is directly mixed in proportion with active material, conductive agent, without adding solvent, is omitted solvent and is made generation in slurry process The situation of grain, and without removing solvent again, this programme suppresses its volumetric expansion in the rigid structure and caking property for ensureing pole piece On the premise of in turn simplify technological process, and cause pole piece thickness and load capacity to become more controllable, industrial scale preferably is big The demand of large-scale production.
Embodiment
The present invention relates to a kind of lithium ion battery electrode piece, by binding agent, conductive agent, active material and collector group Into wherein the quality parts ratio of binding agent, conductive agent and active material is 1-20：0-20：60-99, it is when conductive agent is 0 Do not include conductive agent, wherein binding agent uses polytetrafluoroethylene (PTFE) (PTFE), polytetrafluoroethylene (PTFE) can directly with active material, conductive agent Mixing film in proportion, it is not necessary to add solvent.
Wherein, conductive agent is Super P-Li, acetylene black, graphite, KS-6, carbon ball, CNT, carbon fiber, activated carbon In one or more of combinations, active material is electrode material；Preferably, electrode material be cobalt acid lithium, spinel lithium manganate, Spinel nickel LiMn2O4, multicomponent material, lithium titanate, graphite, nano silicon material, silicon carbon material, LiFePO4, lithium ferric manganese phosphate, One kind in lithium vanadate, wherein multicomponent material are LiNixCoyMnzO2, wherein 0≤x≤1,0≤y≤1,0≤z≤1, according to system The difference of standby battery variety, selects the conductive agent of different categories and active material to prepare electrode slice film.
Wherein, collector is one kind in copper foil, netted copper foil, aluminium foil, netted aluminium foil, utter misery copper foil, utter misery aluminium foil.
A kind of method for preparing lithium ion battery electrode piece, preparation process are as follows：
Conductive agent and active material are pressed 0-20 by step 1：60-99 mass fraction ratio mixing, grinds mixed in mortar Conjunction forms uniform mixture of powders, avoids leaving granular substance；
Step 2 adds the viscous of 1-20 mass fractions into the mixture of powders of well mixed active material and conductive agent Tie agent PTFE, be sufficiently mixed uniformly after grinding slabbing, then by its it is folding roll to obtain uniform and smooth smooth film, It is 5-1000 μm to control gained film thickness；
Film is hot-pressed onto on collector by step 3, hot pressing pressure 0.1-20MPa, and hot pressing temperature is 20-300 DEG C, is made Lithium ion battery electrode piece.
Use PTFE to be mixed as binding agent with active material and conductive agent in this programme, bonding is used as using polytetrafluoroethylene (PTFE) Agent can suppress its volumetric expansion on the premise of the rigid structure of pole piece is ensured, no longer add solvent to make slurry, instead of The effect of solvent mixing, eliminate addition solvent and remove the process of solvent, that is, reduce shadow of the solvent to electrode slice preparation process Ring, improve compacted density, reduce the influence to electrode material chemical property, and pole piece thickness and load capacity are become more Add performance that is controllable, and then improving lithium ion battery；And from process aspect, reduce the step of adding and removing solvent, Processing step is simplified, improves operating efficiency, and also controlled in cost from preparing.
The present invention program is further explained with reference to embodiment.
Embodiment 1：
A kind of lithium ion battery electrode piece, wherein binding agent are PTFE, and conductive agent is acetylene black, and active material is silicon-carbon Composite, collector use copper foil or netted copper foil, and active material can also be nano silicon material, silicon carbon material, specific system Preparation Method is as follows：
500mg Si-C composite materials are weighed, 100mg acetylene blacks, ground and mixed is uniform in mortar, avoids leaving graininess Thing, 100mgPTFE is added after mixing, and mixture is ground into slabbing, and smooth 100 are finally given to its folding rolls μm film.
Above-mentioned film is applied into 10MPa pressure, 90 DEG C push and are layed onto in copper foil current collector, and electrode plates are made.
Embodiment 2：
A kind of lithium ion battery electrode piece, wherein binding agent are PTFE, and conductive agent is Super P-Li, and active material is LiFePO4, collector use aluminium foil or netted aluminium foil, and wherein active material can also be lithium ferric manganese phosphate, using active material as Exemplified by LiFePO4, preparation method is as follows：
800mg LiFePO4s are weighed, 100mg Super P-Li, ground and mixed is uniform in mortar, avoids leaving particle Shape thing, 100mgPTFE is added after mixing, and mixture is ground into slabbing, to its it is folding roll finally give it is smooth 60 μm of film.
Above-mentioned film is applied into 5MPa pressure, 180 DEG C push and are layed onto in aluminum foil current collector, and electrode plates are made.
Embodiment 3：
A kind of lithium ion battery electrode piece, wherein binding agent are PTFE, and conductive agent KS-6, active material is vanadic acid Lithium, collector use utter misery copper foil, and specific preparation method is as follows：
1200mg lithium vanadates are weighed, 100mg KS-6, ground and mixed is uniform in mortar, avoids leaving granular substance, mixes 100mgPTFE is added after even, mixture is ground into slabbing, smooth 110 μm are finally given to its folding rolls Film.
Above-mentioned film is applied into 0.5MPa pressure, 20 DEG C push and are layed onto in utter misery copper foil current collector, and electrode plates are made.
Embodiment 4：
A kind of lithium ion battery electrode piece, wherein binding agent are PTFE, and conductive agent is carbon ball, and active material is cobalt acid Lithium, collector use utter misery aluminium foil, and wherein conductive agent can also be CNT, carbon fiber or activated carbon, and active material may be used also To be spinel nickel LiMn2O4, spinel lithium manganate or lithium titanate, specific preparation method is as follows：
900mg cobalt acid lithiums are weighed, 50mg carbon balls, ground and mixed is uniform in mortar, avoids leaving granular substance, after mixing 50mgPTFE is added, mixture is ground into slabbing, smooth 10 μm of film is finally given to its folding rolls.
Above-mentioned film is applied into 20MPa pressure, 300 DEG C push and are layed onto in utter misery aluminum foil current collector, and electrode plates are made.
Embodiment 5：
A kind of lithium ion battery electrode piece, including binding agent, active material and collector, wherein binding agent are PTFE, Active material is multicomponent material, and multicomponent material formula is LiNixCoyMnzO2, wherein 0≤x≤1,0≤y≤1,0≤z≤1, collection Fluid uses aluminium foil, using active material as LiNiCoMnO2Exemplified by, preparation method is as follows：
Weigh 800mg ternary materials LiNiCoMnO2, grinding is in uniform powder in mortar, avoids leaving graininess Thing, 100mgPTFE is added after mixing, and mixture is ground into slabbing, and smooth 900 are finally given to its folding rolls μm film.
Above-mentioned film is applied into 5MPa pressure, 60 DEG C push and are layed onto in aluminum foil current collector, and electrode plates are made.
Several embodiments of the present invention are described in detail above, but the content is only the preferable implementation of the present invention Example, it is impossible to be considered as the practical range for limiting the present invention.All equivalent changes made according to the present patent application scope and improvement Deng, all should still belong to the present invention patent covering scope within.

Claims (10)

  1. A kind of 1. lithium ion battery electrode piece film, it is characterised in that：It is made up of binding agent and active material, wherein binding agent matter Amount number is 1-20, and active material mass fraction is 60-99.
  2. 2. lithium ion battery electrode piece film according to claim 1, it is characterised in that：The bonding agent is polytetrafluoroethyl-ne Alkene.
  3. 3. lithium ion battery electrode piece film according to claim 1 or 2, it is characterised in that：Also include conductive agent, it is described Conductive agent mass fraction is no more than 20.
  4. 4. lithium ion battery electrode piece film according to claim 3, it is characterised in that：The conductive agent is Super P- One or more of combinations in Li, acetylene black, graphite, KS-6, carbon ball, CNT, carbon fiber, activated carbon.
  5. 5. according to any described lithium ion battery electrode piece film of claim 1 or 2, it is characterised in that：The active material For electrode material；
    Preferably, the electrode material be cobalt acid lithium, spinel lithium manganate, spinel nickel LiMn2O4, multicomponent material, lithium titanate, One kind in graphite, nano silicon material, silicon carbon material, LiFePO4, lithium ferric manganese phosphate, lithium vanadate.
    Preferably, multicomponent material LiNixCoyMnzO2, wherein 0≤x≤1,0≤y≤1,0≤z≤1.
  6. 6. lithium ion battery electrode piece made of any lithium ion battery electrode piece film in a kind of claim 1-5, It is characterized in that：By lithium ion battery electrode piece film cladding on a current collector.
  7. 7. lithium ion battery electrode piece according to claim 6, it is characterised in that：The collector is copper foil, netted One kind in copper foil, aluminium foil, netted aluminium foil, utter misery copper foil, utter misery aluminium foil.
  8. A kind of 8. method for preparing lithium ion battery electrode piece film, it is characterised in that：Preparation process is as follows：
    The active material that step 1 takes mass fraction to be 1-20 is ground into uniform powder；
    Step 2 adds the binding agent that mass fraction is 60-99 into above-mentioned powder, again by rolling after being sufficiently mixed uniformly To uniform and smooth smooth film；
    Preferably, the conductive agent that mass fraction is no more than 20 is added into the active material of step 1, it is well mixed to pulverize End；
    Preferably, gained film thickness is 5-1000 μm in step 2.
  9. A kind of 9. method for preparing lithium ion battery electrode piece, it is characterised in that：Preparation process is as follows：
    The active material that step 1 takes mass fraction to be 1-20 is ground into uniform powder；
    Step 2 adds the binding agent that mass fraction is 60-99 into above-mentioned powder, again by rolling after being sufficiently mixed uniformly To uniform and smooth smooth film；
    The film is hot-pressed onto on the collector by step 3, and lithium ion battery electrode piece is made.
    Preferably, the conductive agent that mass fraction is no more than 20 is added into the active material of step 1, it is well mixed to pulverize End；
    Preferably, gained film thickness is 5-1000 μm in step 2.
    Preferably, hot pressing pressure is 0.1-20MPa in step 3.
    Preferably, hot pressing temperature is 20-300 DEG C in step 3.
  10. 10. application of the lithium ion battery electrode piece in lithium battery positive and negative pole material described in claim 6 or 7, its feature It is：For there is the negative material of volumetric expansion.
CN201710554731.4A 2017-07-10 2017-07-10 A kind of lithium ion battery electrode piece and preparation method thereof and application Pending CN107403933A (en)

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CN108417776A (en) * 2018-05-11 2018-08-17 东莞市创明电池技术有限公司 Battery pole piece and preparation method thereof and lithium ion battery
CN110993885A (en) * 2019-12-19 2020-04-10 佛山市恩力晟和能源科技有限公司 Forming method of electrode for secondary battery
CN112201764A (en) * 2020-01-20 2021-01-08 蜂巢能源科技有限公司 Preparation device and preparation method of battery pole piece
CN112687830A (en) * 2020-12-14 2021-04-20 双登集团股份有限公司 Method for manufacturing lithium ion battery pole plate
CN113206222A (en) * 2021-05-06 2021-08-03 合肥国轩高科动力能源有限公司 Method for preparing lithium battery pole piece with low solvent and prepared pole piece
CN114899355A (en) * 2022-06-29 2022-08-12 深圳市一众自动化技术有限公司 Lithium ion battery electrode and preparation method thereof
CN115332539A (en) * 2022-10-17 2022-11-11 天津普兰能源科技有限公司 Composite material for preparing electrode, preparation method of composite material, electrode and preparation method of electrode

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CN108417776A (en) * 2018-05-11 2018-08-17 东莞市创明电池技术有限公司 Battery pole piece and preparation method thereof and lithium ion battery
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CN114899355A (en) * 2022-06-29 2022-08-12 深圳市一众自动化技术有限公司 Lithium ion battery electrode and preparation method thereof
CN115332539A (en) * 2022-10-17 2022-11-11 天津普兰能源科技有限公司 Composite material for preparing electrode, preparation method of composite material, electrode and preparation method of electrode

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Application publication date: 20171128