CN110224112A - A kind of secondary pore forming method of lithium ion battery - Google Patents

A kind of secondary pore forming method of lithium ion battery Download PDF

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Publication number
CN110224112A
CN110224112A CN201811320937.1A CN201811320937A CN110224112A CN 110224112 A CN110224112 A CN 110224112A CN 201811320937 A CN201811320937 A CN 201811320937A CN 110224112 A CN110224112 A CN 110224112A
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pole piece
creating material
pore
calculated
pore creating
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CN110224112B (en
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张学全
周伟
孙先富
杨行
陈云鹏
孙世界
吕文东
兰海侠
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Shandong Huayi Bi Ke New Energy Ltd By Share Ltd
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Shandong Huayi Bi Ke New Energy Ltd By Share Ltd
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0433—Molding
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of secondary pore forming methods of lithium ion battery, comprising the following steps: pore creating material S1: is thermally formed melt liquid；S2: increase melt liquid immersion or spraying cabinet at the tail of coating machine, soaking box is using melt liquid；S3: prepared anode and cathode slurry is uniformly coated on collector substrate, is passed through spray tank after drying or is passed through soaking box；S4: the pole piece harvest coiled strip after pore creating material will be solidified, by roll squeezer according to normal flow roll-forming；S5: by the good pole piece of roll-in, it is extracted by extraction box, extractant is dried by oven again, or pole piece after roll-in is drenched into oven by hot wind wind, pole piece passes through the heat treatment of high temperature nitrogen atmosphere oven again, and the present invention had not only been able to maintain pole piece high-pressure solid and has improved battery energy density, but also can improve battery pole piece hole uniformity and ensure the method for the performances such as multiplying power, circulation, low temperature, closed pore and shrinkage cavity than regular meeting considerable decrease, improve the effective porosity of pole piece.

Description

A kind of secondary pore forming method of lithium ion battery
Technical field
The present invention relates to technical field of lithium ion, the secondary pore forming method of specially a kind of lithium ion battery.
Background technique
Lithium ion battery has many advantages, such as that high energy density, long service life and voltage are high, is not only in portable electronic In equipment, such as mobile phone, mobile power source, digital camera and the consumer commercially available quick development of notebook, and electronic The emerging markets such as the power categories such as automobile, electric bicycle and electric tool market and energy storage class market have also obtained widely answering With.
In these emerging market field, especially automobile powers using upper, whether the market demand or national policy are led To made higher requirement to the energy force density of power battery.Therefore each enterprise and research universities and colleges are positive and negative by replacing Pole material reduces membrane thicknesses, improves the methods of charging voltage etc. to promote energy density, but these improve energy densities Method is both advantageous and disadvantageous, and great hidden danger is left in terms of cell safety.
The positive/negative plate most crucial for power battery, it is close that ability improves using higher compacted density in many enterprises Degree, for example LiFePO4 is from 1.8g/cm3 in 2011, be increased to 2.5-2.6g/cm3 in 2017, and graphite is from before 1.35-1.5g/cm3 steps up 1.6-1.65g/cm3, and reaching does not influence to improve power electric in the case where security performance as far as possible The purpose of the energy density in pond.But compacted density is higher, pole piece is porous electrode, can generate surface in the case of high-pressure solid and close Hole.Pole piece theoretically vertical depression in roll-in, but practical current roll squeezer steel rod diameter is generally in 600-1200mm, It cannot achieve horizontal direction not stressing deformation.Pole piece is to press up and down simultaneously, and since collector is in centre, two sides active material is thick Degree at 80-180 micron, it appears that it is very thin, but industry use active material particle generally at 0.5-30 microns, therefore and Plurality of layers active material particle is stacked, and the deformation quantity on surface layer is very big when roll-in, and the deformation quantity close to substrate layer is small, passes through The detection of brilliant section, is amplified using SEM, and the porosity that can calculate ectonexine is widely different, and mean porosities are about after roll-in 30%-40%, interior layer porosity is generally all in 45%-55%, and outer layer porosity is generally all in 20%-30%.It is outer by mercury injection method test Layer hole obviously than non-roll-in when reduce very much, and tortuosity increases (mercury ejection time long, residual more), that is to say, that in raising roller It when pressing compacted density, produces a large amount of closed pore and surface layer aperture sharply becomes smaller, lead to the decline of battery multiplying power, cryogenic property Decline is easy analysis lithium, battery cycle life decaying etc. adverse consequences.
Therefore, new pore-creating technique is produced again in the industry, pore creating material is added by various forms, is then reheated after roll-in Pore-creating, such as: the patents such as CN104157827A, CN106848148A and CN103515607A.CN104157827A patent is taken Be the pore creating material that liquid is added inside slurry, form more holes when being coated with baking, but thus improve pole piece Thickness, in subsequent nipping process, this some holes of generation also will appear closed pore and reduce the phenomenon that, than normal pole piece reduce and The ratio of closed pore is bigger, because of the not whole hole that pole piece lacks, the hole on surface layer, therefore this pore forming method is real The closed pore that border obtains is more, and ectonexine Affecting Pore Differential is bigger.What CN103515607A patent was mentioned is made by adding solid Hole agent, is configured to slurry, after pole piece roll-in, by pyrolytic pore creating material, generates more holes, this method can be Pole piece hole is improved to a certain extent, but it is also the same there are the position that internal layer does not need pore-creating, more holes have been made, have been caused Pole piece thickness increases, and reduces battery energy density, does not reach the result for telling that density is desired.It can only improve to a certain extent Battery performance, it is limited for the castering action of energy density.What CN106848148A patent proposed is that pole piece is not also after coating It is just sprayed pore creating material when dry, is entering coating machine oven cooking cycle, is allowing pore creating material to be distributed to pole piece slurry surface layer, in pole after drying The pore-creating of piece surface layer is more, heat resolve pore-creating after roll-in, but this scheme is there is also an apparent problem, is exactly pore-creating Although agent, inside the pole piece of surface layer, pore-creating also results in the rebound of pole piece thickness, although beneficial to the hole of closure again aperture, It is not helped for compressing small hole, other of generation can be discharged directly by these apertures, some holes of generation, also It is that many needs are communicated with the outside world by the hole reduced, has certain effect for reducing Surface Polarization, but still can not solve It certainly keeps improving actually useful porosity in the case of pole piece high-pressure solid.
In view of the above problems, the invention proposes one kind to carry out different journeys to middle layer, surface layer under high compacted density Degree ground pore-creating reaches that surface layer pore-creating is more, and middle layer pore-creating is few by controlling pore creating material adding technology, while not influencing pole piece rebound. It allows the hole reduced scale on surface layer and degree to lighten in roll-in, pressure is allowed to evenly spread to the internal layer of pole piece, allow internal layer deformation Amount becomes larger, and mitigates outer layer deformation, reduces roll-in closed pore and hole reduced scale and degree.By secondary pore-creating, orientation expands The closed hole of the hole and opening reduced.It provides and a kind of be both able to maintain pole piece high-pressure solid to improve the energy content of battery close It spends, and battery pole piece uniformity can be improved to ensure the method for the performances such as multiplying power, circulation, low temperature.
Summary of the invention
Pole piece high-pressure solid had not only been able to maintain the purpose of the present invention is to provide one kind and has improved battery energy density, but also can improve electricity Pond pole piece uniformity ensures the method for the performances such as multiplying power, circulation, low temperature.It is close that this method can guarantee to further increase pole piece compacting In the case of degree, pole piece surface layer hole is uniform and quantity is more, closed pore and shrinkage cavity than regular meeting considerable decrease, it is effective to improve pole piece Porosity, to solve the problems mentioned in the above background technology.
To achieve the above object, the invention provides the following technical scheme: a kind of secondary pore forming method of lithium ion battery, packet Include following steps:
S1: pore creating material is heated to 40~120 DEG C, forms melt liquid；
S2: increasing melt liquid at the tail of coating machine and impregnate or spraying cabinet, and spray tank atomized inside pressure is 0.1~ 100KPa, atomization temperature are 60~130 DEG C, and soaking box is using 40~120 DEG C of melt liquid；
S3: prepared anode and cathode slurry is uniformly coated on collector substrate, after drying, with the speed of 0.01~5 meter per second Degree passes through soaking box, then cooling box by spray tank or with 1~60 m/min of speed, it is ensured that it is 1 that pole piece, which receives nebulisation time, ~300 seconds or soaking time 0.1~30 second, the cooler bin time, which is subject to, to be cooled to pore creating material and solidifies completely；
S4: the pole piece harvest coiled strip after pore creating material will be solidified, by roll squeezer according to normal flow roll-forming, maintaining roller pressure ring Border humid control is not within the scope of pore creating material absorbs water；
S5: the good pole piece of roll-in dries extractant by extraction box extraction time 1~300 second, then by oven, herein Band extractant condensing recovery is recycled；Or pole piece after roll-in is drenched into oven by hot wind wind, hot wind blows leaching treatment temperature 80 It~150 DEG C, handles the time 1~300 second, most of melting pore creating material liquid blowout is recycled, pole piece passes through high temperature nitrogen again The heat treatment of atmosphere oven, it is residual inside pore by being largely adsorbed onto depending on temperature is to correspond to high 5~10 DEG C of pore creating material boiling point Remaining pore creating material is evaporated by the mode of high-boiling, reduces residual to the greatest extent, allows pore creating material that can reach 99.9% or more It is recycled, oven band condensate recycling device, heat treatment time 1~30 minute；
S6: by ready-made pole piece, according to production procedure, process delivers production backward；
S7: taking that pole piece obtained by the 5th step is recorded as atomization respectively plus extraction is calculated as 1-1 and 1-2, atomization heat treatment be calculated as 1-3 and 1-4, impregnate plus extraction be calculated as 1-5 and 1-6, that impregnates heat treatment is calculated as 1-7 and 1-8, with mercury injection method test porosity and Tortuosity makes a record, and pole piece is done profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity with software statistics, does Record easy to remember；
S8: respectively taking 2 for ready-made battery at random, is recorded as atomization respectively plus extraction is calculated as 1-1 and 1-2, atomization heat treatment It is calculated as 1-3 and 1-4, impregnates plus what is extracted is calculated as 1-5 and 1-6, that impregnates heat treatment is calculated as 1-7 and 1-8, after partial volume, meter Energy density is calculated, is made a record, by electric discharge recording capacity at resulting battery testing multiplying power and -20 DEG C.
Preferably, pore creating material is EC, DPC, paraffin, FEC, TCA, dibenzoic acid, Oxybenzone, 40 in the step S1 Any one in alkane, 2- chlorobenzonitrile and 2,3-butanediol, but it is not limited to these pore creating materials.
Preferably, the EC, DPC, 2,3-butanediol and the corresponding extractant of tetracontane are respectively DMC, curing Carbon, ethyl alcohol and dimethyl methyl acid amide, but it is not limited to the solvent of these types.
Preferably, spray tank atomized inside preferred pressure is 1~10KPa in the step S2, is atomized preferable temperature 80 ~120 DEG C, for the melt liquid preferable temperature that soaking box uses for 60~100 DEG C, melt liquid viscosity is less than 100mPa*s.
Preferably, receive that the spraying preferred time is 5~180 seconds or soaking time is 0.5~5 second in the step S3, Pole piece after immersion blows leaching with nitrogen, by the pore creating material melt of excess surface it is few as far as possible remain in pole piece, by pole Piece is sufficiently cooled to pore creating material and solidifies completely.
Preferably, roll in the step S4 and carried out in roll squeezer, take pole piece and facility environment moisture to control and add sternly To < 2%RH, rolling condition is 0.5-3.0 megapascal, and the speed of calendering is 10~40m/min, form pole piece with a thickness of 90~ 190um, compacted density are as follows: 1.6~1.68g/cm of graphite cathode3, positive 2.7~2.8g/cm of LiFePO43, positive ternary 3.6 ~3.75g/cm3, positive 3.1~3.2g/cm of LiMn2O43, but it is not limited to these thickness and compacted density.
It preferably, is 10~120 seconds by the preferred time value that extraction box extracts in the step S5, melting that treated Liquid viscosity is less than 50mPa*S, and the preferred time of processing is 10~180 seconds, oven band condensate recycling device, when being heat-treated preferred Between be 3~20 minutes.
The difference that method provided by the invention and comparison patent have essence is that the present invention then is added after pole piece drying Add pore creating material, pore creating material be laterally homogeneously added in the surface layer hole of pole piece, Axinlly nonuniform be added to pole piece surface layer, In middle layer and internal layer.
It is solid under pore creating material room temperature of the invention, is the liquid under molten condition at 40-80 DEG C, is superfused by pole piece Melt liquid, immersion is adsorbed onto the hole of pole piece.But it is not limited to impregnate the mode of absorption, it is similar with the patent families of company, It is added using spray pattern, difference is the solution of the not instead of pore creating material of spraying spray, and pore creating material itself is in liquid, herein not It repeats.
Pore creating material of the present invention is cooling after being added in pole piece hole, then passes through roll-in, then extract by corresponding solvent It takes or after hot wind blows leaching, crosses high temperature oven drying.
The residual of pore creating material selected by the present invention is a small amount of, on battery performance without influence.
After pore creating material of the invention enters the pore interior cooling on pole piece surface layer, it can effectively be essentially filled with surface layer hole Gap, and be partially filled with middle layer hole artificially manufactures the interior of a highdensity surface layer, the middle layer of middle density and low-density Layer.It can be to have manufactured the low difficult compression of a porosity in roll-in forefathers by pressure conduction to pole piece internal layer in roll-in Pole piece surface layer, by pressure conduction to internal layer, inside in table three layers of formation, one transition zone, the Content of Pore-forming Agents on surface layer is most, most Hardly possible compression, middle layer pore creating material is few, and more difficult compression, internal layer does not have pore creating material, compressible.It is adjusted by this compression difficulty, it will Surface layer is big by pressure in common pore-creating or nipping process, and internal layer is solved by the small problem of pressure, and pressure is effectively conducted to Pole piece internal layer.Although still outer layer stress is big when roll-in, the compression of outer layer difficulty, internal layer stress is smaller, but internal layer is compressible, Therefore the ectonexine deformation quantity that the ratio of adjustment roll-in and pore creating material can be obtained finally is very close to state, largely Solves the problems, such as the compression ratio of ectonexine.The present invention is obtained by hundreds of related adding technologies and roller compaction roller compaction coordinative experiments The range to work well.Be not professional and technical personnel in the field can it is apparent it is contemplated that, this field profession skill How after being compressed art personnel consider it is more how to manufacture more holes, or pore-creating again.Other methods reduce table Layer deformation quantity, such as: it with the roll squeezer of larger diameter, allows dynamics close to vertical direction roll-in, also has more using repeatedly coating The mode of secondary roll-in, but coating process difficulty is big before and after this mode, surface density control is very difficult, but all can not The problem of efficiently solving ectonexine deformation quantity.The present invention is to reduce outer layer deformation by technology controlling and process ectonexine compression factor Amount improves outer layer porosity, is that solve this from root contradictory.
Pore creating material of the invention is distributed in some extent in the pre-existent pore generated when coating baking, and there is no tradition After the roll-in of patent the problem of the blind hole and closed pore of pore-creating, decomposition will not allow pole piece thickness to rebound.Pore creating material of the invention It is in oriented attachment to pre-existent pore, therefore the pore-creating in extraction or hot wind leaching or thermal decomposition, is original when releasing baking Hole, at the same can closed pore will be become through-hole, the hole of diminution is become larger, rather than the pore-creating everywhere inside patent before or with Machine pore-creating.
The present invention realizes orientation pore-creating, lays the foundation for the pole piece of more high compacted density, realize the prior art without The performance that method reaches.The pole piece porosity of the prior art is at 30%~40% or so, and surface just closed pore or shrinkage cavity can not Solve the problems, such as that internal layer and outer layer porosity difference are big, although causing whole porosity big, actually available porosity is only Only there was only surface (ectonexine hole is a large amount of series-parallel form presence), though whole porosity 30%~40%, it is actual effectively Porosity only has 20%~30%(surface porosity factor generally all 25%~28% or so), the mean porosities of pole piece exist in the present invention When 25%~30%, effective drainage porosity can also reach 23%~28%, it is meant that in the case of same effective drainage porosity, place of the invention The positive/negative plate of reason can apply the material (account for active material space about 12%) in about space 8% more, that is, increase dressing about 12% or so Active material, at least improve 12% energy density.
The first purpose of the invention is to provide the pole pieces (porous electrode) before a kind of roll-in, including active material, bonding Agent, solvent and pore creating material, wherein pore creating material can be organic compound one or more of of the fusing point at 40-80 DEG C.This The pore creating material of invention can choose EC ethylene carbonate, DPC, paraffin etc., and corresponding extractant is respectively DMC, DMC and curing Carbon etc., but it is not limited to these types of pore creating material and extractant.
A second object of the present invention is to provide a kind of lithium ion battery, should by above-mentioned pole piece, thermally treated, film-making, The processes such as assembly, fluid injection are prepared, wherein and the mean porosities of pole piece are 25%~30%, effective drainage porosity 23%~28%, Have same low temperature, multiplying power and cycle performance with the battery of low tapped density, energy density promotes the processing of 6%-12%(single electrode About 6%, about 12%) positive and negative anodes are handled.
Third object of the present invention is to provide a kind of lithium ion battery, which includes battery case and is sealed in the electricity The intracorporal electrode group of pond shell and electrolyte；The electrode group include anode, cathode and positioned at anode and cathode between every Film, described is above-mentioned lithium ion battery.This purpose is the industry well-known technique that those skilled in the art obviously can be realized, herein It does not repeat.
Compared with prior art, the beneficial effects of the present invention are: the present invention, which had both been able to maintain pole piece high-pressure solid, improves battery energy Metric density, and battery pole piece uniformity can be improved ensure the method for the performances such as multiplying power, circulation, low temperature.This method can guarantee into In the case of one step improves pole piece compaction density, pole piece surface layer hole is uniform and quantity is more, under the ratio regular meeting of closed pore and shrinkage cavity is very big Drop, improves the effective porosity of pole piece.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not For limiting the present invention.
The positive and negative anodes active material is not particularly limited in the present invention, can in the prior art can be commercially available it is any Positive and negative anodes active material, can using can be commercially available all positive active materials, such as LiFePO4, Li3V2 (PO4) 3, LiMn2O4, LiMnO2, LiNiO2, LiCoO2, LiVPO4F, LiFeO2；Or ternary system Li1 adds aL1-b-cMbNcO2, a, B, c respectively indicates molal quantity, wherein -0.1≤a≤0.2,0≤b≤1,0≤c≤1,0≤b add c≤1.0, L, M, N Co, It is one or more of in Mn, Ni, Al, Mg, Ga, Sc, Ti, V, Cr, Fe, Cu and Zn.All cathode that can be commercially available can be used to live Property substance, such as artificial graphite, natural graphite, silicon carbon material, lithium titanate.
The type of the positive and negative electrode current collector is known to those skilled in the art, for example, can selected from aluminium foil, copper foil, Punching foil etc..Use aluminium foil as positive electrode collector in a specific embodiment of the invention, copper foil is negative current collector.
The present invention, without particular/special requirement, is referred to prior art progress, generally to the preparation method of the lithium ion battery For, it separates anode and cathode winding to form electrode group by diaphragm, electrode group is placed in battery case, electrolyte is added, Then it seals, wherein winding and the method for sealing is well known to those skilled in the art.The dosage of electrolyte is conventional amount used.? Obtain lithium ion battery provided by the invention.The conventional steps such as subsequent also ageing, chemical conversion, details are not described herein.
The present invention pertains only to improve the pole piece processing technology of prior art lithium ion secondary battery, therefore to lithium ion two Other the Nomenclature Composition and Structure of Complexes of primary cell are not particularly limited.Such as it is not special to the anode, diaphragm and electrolyte of battery All types of anodes, diaphragm and the electrolyte that can be used in a lithium ion secondary battery can be used in limitation.This field it is general Logical technical staff can instruct according to prior art, easily can select and prepare lithium ion secondary of the present invention Anode, diaphragm and the electrolyte of battery, and it is made of the invention by cathode positive, of the invention, diaphragm and the electrolyte Lithium ion secondary battery, details are not described herein.
Embodiment 1:
A kind of secondary pore forming method of lithium ion battery, comprising the following steps:
S1: pore creating material is EC by the first step, is thermally formed melt liquid, corresponding extractant is respectively DMC；
S2: increasing melt liquid immersion or spraying cabinet at the tail of coating machine, and spray tank atomized inside pressure is 1KPa, 100 DEG C of atomization temperature, soaking box is using 80 DEG C；
S3: prepared cathode graphite slurry is uniformly coated on collector substrate, after drying, is passed through with 2 meter per second speed Spray tank or with 40 ms/min of speed by soaking box, receive that the spraying time is 5 seconds or soaking time is 0.5 second, after immersion Pole piece blow leaching with nitrogen, pole piece is sufficiently cooled to pore creating material and is solidified completely；
S4: the pole piece harvest coiled strip after pore creating material will be solidified, by roll squeezer according to normal flow roll-forming, maintaining roller pressure ring Border humid control takes pole piece and facility environment moisture to control plus sternly to < 2%RH, stone within the scope of pore creating material does not absorb water Black cathode compacted density accomplishes 1.68g/cm3；
S5: the good pole piece of roll-in dries extractant by extraction box extraction time 60 seconds, then by oven, herein band extraction Agent condensing recovery is taken to be recycled；Or pole piece after roll-in is drenched into oven by hot nitrogen wind, treatment temperature 150 is drenched in hot nitrogen air-blowing DEG C, it handles the time 120 seconds, most of melting pore creating material liquid blowout is recycled with hot nitrogen, pole piece passes through high temperature nitrogen again 255 DEG C of atmosphere oven heat treatments, heat treatment time 20 minutes；
S6: by ready-made pole piece, according to production procedure, process delivers production backward, mixes manganese anode using ternary, is formulated with workshop three Member mixes manganese cell, and adjustment surface density reaches reasonable excessive ratio, is made into battery；
S7: taking that pole piece obtained by the 5th step is recorded as atomization respectively plus extraction is calculated as 1-1 and 1-2, atomization heat treatment be calculated as 1-3 and 1-4, impregnate plus extraction be calculated as 1-5 and 1-6, that impregnates heat treatment is calculated as 1-7 and 1-8, with mercury injection method test porosity and Tortuosity makes a record, and pole piece is done profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity (3 etc. with software statistics Divide thickness), it makes a record；
S8: respectively taking 2 for ready-made battery at random, is recorded as atomization respectively plus extraction is calculated as 1-1 and 1-2, atomization heat treatment It is calculated as 1-3 and 1-4, impregnates plus what is extracted is calculated as 1-5 and 1-6, that impregnates heat treatment is calculated as 1-7 and 1-8, after partial volume, meter It calculates energy density (under the conditions of same shell), makes a record, electric discharge recording at resulting battery testing multiplying power and -20 DEG C is held Amount.
Embodiment 2:
A kind of secondary pore forming method of lithium ion battery, comprising the following steps:
S1: it is tetracontane by pore creating material, is thermally formed melt liquid, corresponding extractant is respectively dodecane；
S2: increasing melt liquid immersion at the tail of coating machine or spraying cabinet, spray tank atomized inside pressure are 10KPa, 120 DEG C of atomization temperature, soaking box is using 100 DEG C；
S3: prepared cathode graphite slurry is uniformly coated on collector substrate, after drying, with 0.05 meter per second speed By spray tank or with 6 ms/min of speed by soaking box, receive that the spraying time is 180 seconds or soaking time is 5 seconds, leaching Pole piece after bubble blows leaching with nitrogen, and pole piece is sufficiently cooled to pore creating material and is solidified completely；
S4: the pole piece harvest coiled strip after pore creating material will be solidified, by roll squeezer according to normal flow roll-forming, maintaining roller pressure ring Border humid control takes pole piece and facility environment moisture to control plus sternly to < 2%RH, stone within the scope of pore creating material does not absorb water Black cathode compacted density accomplishes 1.60g/cm3；
S5: the good pole piece of roll-in dries extractant by extraction box extraction time 120 seconds, then by oven, herein band extraction Agent condensing recovery is taken to be recycled；Or pole piece after roll-in is drenched into oven by hot nitrogen wind, treatment temperature 120 is drenched in hot nitrogen air-blowing DEG C, it handles the time 180 seconds, most of melting pore creating material liquid blowout is recycled with hot nitrogen, pole piece passes through high temperature nitrogen again 155 DEG C of atmosphere oven heat treatments, heat treatment time 5 minutes；
S6: by ready-made pole piece, according to production procedure, process delivers production backward.Manganese anode is mixed using ternary, is formulated with workshop three Member mixes manganese cell, and adjustment surface density reaches reasonable excessive ratio, is made into battery；
S7: taking that pole piece obtained by the 5th step is recorded as atomization respectively plus extraction is calculated as 2-1 and 2-2, atomization heat treatment be calculated as 2-3 and 2-4, impregnate plus extraction be calculated as 2-5 and 2-6, that impregnates heat treatment is calculated as 2-7 and 2-8, with mercury injection method test porosity and Tortuosity makes a record, and pole piece is done profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity (3 etc. with software statistics Divide thickness), it makes a record；
S8: respectively taking 2 for ready-made battery at random, is recorded as atomization respectively plus extraction is calculated as 2-1 and 2-2, atomization heat treatment It is calculated as 2-3 and 2-4, impregnates plus what is extracted is calculated as 2-5 and 2-6, that impregnates heat treatment is calculated as 2-7 and 2-8, after partial volume, meter It calculates energy density (under the conditions of same shell), makes a record, electric discharge recording at resulting battery testing multiplying power and -20 DEG C is held Amount.
Embodiment 3:
A kind of secondary pore forming method of lithium ion battery, comprising the following steps:
S1: it is 2- chlorobenzonitrile by pore creating material, is thermally formed melt liquid, corresponding extractant is respectively ethyl alcohol；
S2: increasing melt liquid immersion or spraying cabinet at the tail of coating machine, and spray tank atomized inside pressure is 5KPa, 80 DEG C of atomization temperature, soaking box is using 60 DEG C；
S3: prepared positive LiFePO4 slurry is uniformly coated on collector substrate, after drying, with 0.5 meter per second speed Degree by soaking box, receives that the spraying time is 30 seconds or soaking time is 1 second by spray tank or with 25 ms/min of speed, Pole piece after immersion blows leaching with nitrogen, and pole piece is sufficiently cooled to pore creating material and is solidified completely；
S4: the pole piece harvest coiled strip after pore creating material will be solidified, by roll squeezer according to normal flow roll-forming, maintaining roller pressure ring Border humid control takes pole piece and facility environment moisture to control plus sternly to < 2%RH within the scope of pore creating material does not absorb water, just Pole iron phosphate lithium positive pole compacted density accomplishes 2.7g/cm3；
S5: the good pole piece of roll-in dries extractant by extraction box extraction time 10 seconds, then by oven, herein band extraction Agent condensing recovery is taken to be recycled；Or pole piece after roll-in is drenched into oven by hot nitrogen wind, treatment temperature 80 is drenched in hot nitrogen air-blowing DEG C, it handles the time 60 seconds, most of melting pore creating material liquid blowout is recycled with hot nitrogen, pole piece passes through high temperature nitrogen again 240 DEG C of atmosphere oven heat treatments, heat treatment time 3 minutes；
S6: by ready-made pole piece, according to production procedure well known to industry, process delivers production backward.Using common graphite cathode, adjust Whole face density reaches reasonable excessive ratio, is made into battery；
S7: taking that pole piece obtained by the 5th step is recorded as atomization respectively plus extraction is calculated as 3-1 and 3-2, atomization heat treatment be calculated as 3-3 and 3-4, impregnate plus extraction be calculated as 3-5 and 3-6, that impregnates heat treatment is calculated as 3-7 and 3-8, with mercury injection method test porosity and Tortuosity makes a record, and pole piece is done profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity (3 etc. with software statistics Divide thickness), it makes a record；
S8: respectively taking 2 for ready-made battery at random, is recorded as atomization respectively plus extraction is calculated as 3-1 and 3-2, atomization heat treatment It is calculated as 3-3 and 3-4, impregnates plus what is extracted is calculated as 3-5 and 3-6, that impregnates heat treatment is calculated as 3-7 and 3-8, after partial volume, meter It calculates energy density (under the conditions of same shell), makes a record, electric discharge recording at resulting battery testing multiplying power and -20 DEG C is held Amount.
Embodiment 4:
A kind of secondary pore forming method of lithium ion battery, comprising the following steps:
S1: it is 2,3- butanediol by pore creating material, is thermally formed melt liquid, corresponding extractant is respectively ethyl alcohol；
S2: increasing melt liquid immersion or spraying cabinet at the tail of coating machine, and spray tank atomized inside pressure is 2KPa, 110 DEG C of atomization temperature, soaking box is using 80 DEG C；
S3: prepared positive LiFePO4 slurry is uniformly coated on collector substrate, after drying, with 1.5 meter per seconds speed Degree by soaking box, receives that the spraying time is 30 seconds or soaking time is 3 seconds by spray tank or with 35 ms/min of speed, Pole piece after immersion blows leaching with nitrogen, and pole piece is sufficiently cooled to pore creating material and is solidified completely；
S4: the pole piece harvest coiled strip after pore creating material will be solidified, by roll squeezer according to normal flow roll-forming, maintaining roller pressure ring Border humid control takes pole piece and facility environment moisture to control plus sternly to < 2%RH within the scope of pore creating material does not absorb water, just Pole iron phosphate lithium positive pole compacted density accomplishes 2.6g/cm3；
S5: the good pole piece of roll-in dries extractant by extraction box extraction time 60 seconds, then by oven, herein band extraction Agent condensing recovery is taken to be recycled；Or pole piece after roll-in is drenched into oven by hot nitrogen wind, treatment temperature 150 is drenched in hot nitrogen air-blowing DEG C, it handles the time 20 seconds, most of melting pore creating material liquid blowout is recycled with hot nitrogen, pole piece passes through high temperature nitrogen again 188 DEG C of atmosphere oven heat treatments, heat treatment time 15 minutes；
S6: by ready-made pole piece, according to production procedure, process delivers production backward, using common graphite cathode, adjusts surface density and reaches To reasonable excessive ratio, it is made into battery；
S7: taking that pole piece obtained by the 5th step is recorded as atomization respectively plus extraction is calculated as 4-1 and 4-2, atomization heat treatment be calculated as 4-3 and 4-4, impregnate plus extraction be calculated as 4-5 and 4-6, that impregnates heat treatment is calculated as 4-7 and 4-8, with mercury injection method test porosity and Tortuosity makes a record, and pole piece is done profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity (3 etc. with software statistics Divide thickness), it makes a record；
S8: respectively taking 2 for ready-made battery at random, is recorded as atomization respectively plus extraction is calculated as 4-1 and 4-2, atomization heat treatment It is calculated as 4-3 and 4-4, impregnates plus what is extracted is calculated as 4-5 and 4-6, that impregnates heat treatment is calculated as 3-7 and 3-8, after partial volume, meter It calculates energy density (under the conditions of same shell), makes a record, electric discharge recording at resulting battery testing multiplying power and -20 DEG C is held Amount.
Embodiment 5:
A kind of secondary pore forming method of lithium ion battery, comprising the following steps:
S1: pore creating material is 2,3- butanediol by the first step, is thermally formed melt liquid, corresponding extractant is respectively ethyl alcohol；
S2: increasing melt liquid immersion or spraying cabinet at the tail of coating machine, and spray tank atomized inside pressure is 2KPa, 100 DEG C of atomization temperature, soaking box is using 70 DEG C；
S3: prepared positive LiFePO4 slurry is uniformly coated on collector substrate, after drying, with 0.2 meter per second speed Degree by soaking box, receives that the spraying time is 100 seconds or soaking time is 5 seconds by spray tank or with 15 ms/min of speed, Pole piece after immersion blows leaching with nitrogen, and pole piece is sufficiently cooled to pore creating material and is solidified completely；
S4: the pole piece harvest coiled strip after pore creating material will be solidified, by roll squeezer according to normal flow roll-forming, maintaining roller pressure ring Border humid control takes pole piece and facility environment moisture to control plus sternly to < 2%RH, adopt within the scope of pore creating material does not absorb water With rolling condition commonly used in the art, tertiary cathode compacted density accomplishes 3.75g/cm3；
S5: the good pole piece of roll-in dries extractant by extraction box extraction time 100 seconds, then by oven, herein band extraction Agent condensing recovery is taken to be recycled；Or pole piece after roll-in is drenched into oven by hot nitrogen wind, treatment temperature 100 is drenched in hot nitrogen air-blowing DEG C, it handles the time 150 seconds, most of melting pore creating material liquid blowout is recycled with hot nitrogen, pole piece passes through high temperature nitrogen again 188 DEG C of atmosphere oven heat treatments, heat treatment time 5 minutes；
S6: by ready-made pole piece, according to production procedure, process delivers production backward, using common graphite cathode, adjusts surface density and reaches To reasonable excessive ratio, it is made into battery；
S7: taking that pole piece obtained by the 5th step is recorded as atomization respectively plus extraction is calculated as 5-1 and 5-2, atomization heat treatment be calculated as 5-3 and 5-4, impregnate plus extraction be calculated as 5-5 and 5-6, that impregnates heat treatment is calculated as 5-7 and 5-8, with mercury injection method test porosity and Tortuosity makes a record, and pole piece is done profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity (3 etc. with software statistics Divide thickness), it makes a record；
S8: respectively taking 2 for ready-made battery at random, is recorded as atomization respectively plus extraction is calculated as 5-1 and 5-2, atomization heat treatment It is calculated as 5-3 and 5-4, impregnates plus what is extracted is calculated as 5-5 and 5-6, that impregnates heat treatment is calculated as 5-7 and 5-8, after partial volume, meter It calculates energy density (under the conditions of same shell), makes a record, electric discharge recording at resulting battery testing multiplying power and -20 DEG C is held Amount.
Embodiment 6:
A kind of secondary pore forming method of lithium ion battery, comprising the following steps:
S1: it is EC by pore creating material, is thermally formed melt liquid, corresponding extractant is respectively DMC；
S2: increasing melt liquid immersion or spraying cabinet at the tail of coating machine, and spray tank atomized inside pressure is 5KPa, 110 DEG C of atomization temperature, soaking box is using 90 DEG C；
S3: prepared positive LiFePO4 slurry is uniformly coated on collector substrate, after drying, with 0.5 meter per second speed Degree by soaking box, receives that the spraying time is 30 seconds or soaking time is 3 seconds by spray tank or with 30 ms/min of speed, Pole piece after immersion blows leaching with nitrogen, and pole piece is sufficiently cooled to pore creating material and is solidified completely；
S4: the pole piece harvest coiled strip after pore creating material will be solidified, by roll squeezer according to normal flow roll-forming, maintaining roller pressure ring Border humid control takes pole piece and facility environment moisture to control plus sternly to < 2%RH, adopt within the scope of pore creating material does not absorb water With rolling condition commonly used in the art, tertiary cathode compacted density accomplishes 3.6g/cm3；
S5: the good pole piece of roll-in dries extractant by extraction box extraction time 120 seconds, then by oven, herein band extraction Agent condensing recovery is taken to be recycled；Or pole piece after roll-in is drenched into oven by hot nitrogen wind, treatment temperature 120 is drenched in hot nitrogen air-blowing DEG C, it handles the time 120 seconds, most of melting pore creating material liquid blowout is recycled with hot nitrogen, pole piece passes through high temperature nitrogen again 253 DEG C of atmosphere oven heat treatments, heat treatment time 15 minutes；
S6: by ready-made pole piece, according to production procedure, process delivers production backward.Using common graphite cathode, adjusts surface density and reach To reasonable excessive ratio, it is made into battery；
S7: taking that pole piece obtained by the 5th step is recorded as atomization respectively plus extraction is calculated as 6-1 and 6-2, atomization heat treatment be calculated as 6-3 and 6-4, impregnate plus extraction be calculated as 6-5 and 6-6, that impregnates heat treatment is calculated as 6-7 and 6-8, with mercury injection method test porosity and Tortuosity makes a record, and pole piece is done profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity (3 etc. with software statistics Divide thickness), it makes a record；
S8: respectively taking 2 for ready-made battery at random, is recorded as atomization respectively plus extraction is calculated as 6-1 and 6-2, atomization heat treatment It is calculated as 6-3 and 6-4, impregnates plus what is extracted is calculated as 6-5 and 6-6, that impregnates heat treatment is calculated as 6-7 and 6-8, after partial volume, meter It calculates energy density (under the conditions of same shell), makes a record, electric discharge recording at resulting battery testing multiplying power and -20 DEG C is held Amount.
Embodiment 7:
A kind of secondary pore forming method of lithium ion battery, comprising the following steps:
S1: it is EC by pore creating material, is thermally formed melt liquid, corresponding extractant is respectively DMC；
S2: increasing melt liquid immersion at the tail of coating machine or spraying cabinet, spray tank atomized inside pressure are 10KPa, 120 DEG C of atomization temperature, soaking box is using 100 DEG C；
S3: prepared positive LiFePO4 slurry is uniformly coated on collector substrate, after drying, with 0.1 meter per second speed Degree by soaking box, receives that the spraying time is 150 seconds or soaking time is 5 seconds by spray tank or with 10 ms/min of speed, Pole piece after immersion blows leaching with nitrogen, and pole piece is sufficiently cooled to pore creating material and is solidified completely；
S4: the pole piece harvest coiled strip after pore creating material will be solidified, by roll squeezer according to normal flow roll-forming, maintaining roller pressure ring Border humid control takes pole piece and facility environment moisture to control plus sternly to < 2%RH, adopt within the scope of pore creating material does not absorb water With rolling condition commonly used in the art, lithium manganate cathode compacted density accomplishes 3.2g/cm3；
S5: the good pole piece of roll-in dries extractant by extraction box extraction time 100 seconds, then by oven, herein band extraction Agent condensing recovery is taken to be recycled；Or pole piece after roll-in is drenched into oven by hot nitrogen wind, treatment temperature 130 is drenched in hot nitrogen air-blowing DEG C, it handles the time 30 seconds, most of melting pore creating material liquid blowout is recycled with hot nitrogen, pole piece passes through high temperature nitrogen again 256 DEG C of atmosphere oven heat treatments, heat treatment time 5 minutes；
S6: by ready-made pole piece, according to production procedure, process delivers production backward.Using common graphite cathode, adjusts surface density and reach To reasonable excessive ratio, it is made into battery；
S7: taking that pole piece obtained by the 5th step is recorded as atomization respectively plus extraction is calculated as 7-1 and 7-2, atomization heat treatment be calculated as 7-3 and 7-4, impregnate plus extraction be calculated as 7-5 and 7-6, that impregnates heat treatment is calculated as 7-7 and 7-8, with mercury injection method test porosity and Tortuosity makes a record, and pole piece is done profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity (3 etc. with software statistics Divide thickness), it makes a record；
S8: ready-made battery respectively takes 2 at random, is recorded as atomization respectively plus extraction is calculated as 7-1 and 7-2, atomization heat treatment meter It for 7-3 and 7-4, impregnates plus what is extracted is calculated as 7-5 and 7-6, that impregnates heat treatment is calculated as 7-7 and 7-8, after partial volume, calculates Energy density (under the conditions of same shell), makes a record, and electric discharge recording at resulting battery testing multiplying power and -20 DEG C is held Amount.
Embodiment 8:
A kind of secondary pore forming method of lithium ion battery, comprising the following steps:
S1: it is tetracontane by pore creating material, is thermally formed melt liquid, corresponding extractant is respectively dodecane；
S2: increasing melt liquid immersion or spraying cabinet at the tail of coating machine, and spray tank atomized inside pressure is 1KPa, 110 DEG C of atomization temperature, soaking box is using 100 DEG C；
S3: prepared positive LiFePO4 slurry is uniformly coated on collector substrate, after drying, with 0.3 meter per second speed Degree by soaking box, receives that the spraying time is 60 seconds or soaking time is 3 seconds by spray tank or with 30 ms/min of speed, Pole piece after immersion blows leaching with nitrogen, and pole piece is sufficiently cooled to pore creating material and is solidified completely；
S4: the pole piece harvest coiled strip after pore creating material will be solidified, by roll squeezer according to normal flow roll-forming, maintaining roller pressure ring Border humid control takes pole piece and facility environment moisture to control plus sternly to < 2%RH, manganese within the scope of pore creating material does not absorb water Sour lithium anode compacted density accomplishes 3.1g/cm3；
S5: the good pole piece of roll-in dries extractant by extraction box extraction time 90 seconds, then by oven, herein band extraction Agent condensing recovery is taken to be recycled；Or pole piece after roll-in is drenched into oven by hot nitrogen wind, treatment temperature 140 is drenched in hot nitrogen air-blowing DEG C, it handles the time 160 seconds, most of melting pore creating material liquid blowout is recycled with hot nitrogen.Pole piece passes through high temperature nitrogen again 160 DEG C of atmosphere oven heat treatments, heat treatment time 15 minutes；
S6: by ready-made pole piece, according to production procedure, process delivers production backward.Using common graphite cathode, adjusts surface density and reach To reasonable excessive ratio, it is made into battery；
S7: taking that pole piece obtained by the 5th step is recorded as atomization respectively plus extraction is calculated as 8-1 and 8-2, atomization heat treatment be calculated as 8-3 and 8-4, impregnate plus extraction be calculated as 8-5 and 8-6, that impregnates heat treatment is calculated as 8-7 and 8-8, with mercury injection method test porosity and Tortuosity makes a record, and pole piece is done profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity (3 etc. with software statistics Divide thickness), it makes a record；
S8: respectively taking 2 for ready-made battery at random, is recorded as atomization respectively plus extraction is calculated as 7-1 and 7-2, atomization heat treatment It is calculated as 7-3 and 7-4, impregnates plus what is extracted is calculated as 7-5 and 7-6, that impregnates heat treatment is calculated as 7-7 and 7-8, after partial volume, meter It calculates energy density (under the conditions of same shell), makes a record, electric discharge recording at resulting battery testing multiplying power and -20 DEG C is held Amount.
Comparative example 1:
Battery is made according to normal production procedure.Anode mixes the anode of manganese using the ternary that Examples 1 and 2 use, and use is same The anode of proportion, cathode are accordingly adjusted to match according to conventional progress, surface density, are made into 18650 batteries.
Take normal negative electrode tab (compacted density 1.55g/cm3) with mercury injection method porosity and tortuosity are tested, it makes a record.It will Pole piece does profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity (3 etc. divide thickness) with software statistics, makes a record.
After ready-made battery partial volume, calculates energy density (under the conditions of same shell), make a record.By resulting electricity Electric discharge recording capacity at multiplying power and -20 DEG C is tested in pond.
Comparative example 2:
Battery is made according to normal production procedure.Anode use LiFePO4 anode, with the same proportion of embodiment 3 and 4 Anode, cathode is according to common cathode 1.55g/cm3Conventional to carry out, surface density is accordingly adjusted to match, and is made into 18650 batteries.
Take positive plate (compacted density 2.35g/cm3) with mercury injection method porosity and tortuosity are tested, it makes a record.By pole piece Profile analysis is done, using low power SEM, upper, middle and lower layer porosity (3 etc. divide thickness) is analyzed with software statistics, makes a record.
After ready-made battery partial volume, calculates energy density (under the conditions of same shell), make a record.By resulting electricity Electric discharge recording capacity at multiplying power and -20 DEG C is tested in pond.
Comparative example 3:
Battery is made according to normal production procedure.Anode use ternary anode, with the same proportion of embodiment 5 and 6 just Pole, cathode is according to common cathode 1.55g/cm3Conventional to carry out, surface density is accordingly adjusted to match, and is made into 18650 batteries.
Take positive plate (compacted density 3.45g/cm3) with mercury injection method porosity and tortuosity are tested, it makes a record.By pole piece Profile analysis is done, using low power SEM, upper, middle and lower layer porosity (3 etc. divide thickness) is analyzed with software statistics, makes a record.
After ready-made battery partial volume, calculates energy density (under the conditions of same shell), make a record.By resulting electricity Electric discharge recording capacity at multiplying power and -20 DEG C is tested in pond.
Comparative example 4:
Battery is made according to normal production procedure.Anode use LiMn2O4 anode, with the same proportion of embodiment 7 and 8 Anode, cathode is according to common cathode 1.55g/cm3Conventional to carry out, surface density is accordingly adjusted to match, and is made into 18650 batteries.
Take positive plate (compacted density 2.9g/cm3) with mercury injection method porosity and tortuosity are tested, it makes a record.By pole piece Profile analysis is done, using low power SEM, upper, middle and lower layer porosity (3 etc. divide thickness) is analyzed with software statistics, makes a record.
After ready-made battery partial volume, calculates energy density (under the conditions of same shell), make a record.By resulting electricity Electric discharge recording capacity at multiplying power and -20 DEG C is tested in pond.
Comparative example 5:
Pole piece and battery are done according to CN106848148A scheme.Anode is all made of the anode that the ternary that embodiment 1 uses mixes manganese, uses The anode of same proportion, cathode are handled according to patent, and surface density is accordingly adjusted to match, and are made into 18650 batteries.
Take gained negative electrode tab (compacted density 1.55g/cm3) with mercury injection method porosity and tortuosity are tested, it makes a record.It will Pole piece does profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity (3 etc. divide thickness) with software statistics, makes a record.
After ready-made battery partial volume, calculates energy density (under the conditions of same shell), make a record.By resulting electricity Electric discharge recording capacity at multiplying power and -20 DEG C is tested in pond.
Comparative example 6:
Pole piece and battery are done according to CN103515607A scheme.Anode is all made of the anode that the ternary that embodiment 1 uses mixes manganese, uses The anode of same proportion, cathode are handled according to patent, and surface density is accordingly adjusted to match, and are made into 18650 batteries.
Take gained negative electrode tab (compacted density 1.55g/cm3) with mercury injection method porosity and tortuosity are tested, it makes a record.It will Pole piece does profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity (3 etc. divide thickness) with software statistics, makes a record.
After ready-made battery partial volume, calculates energy density (under the conditions of same shell), make a record.By resulting electricity Electric discharge recording capacity at multiplying power and -20 DEG C is tested in pond.
Comparative example 7:
Pole piece and battery are done according to CN104157827A scheme, anode is all made of the anode that the ternary that embodiment 1 uses mixes manganese, uses The anode of same proportion, cathode are handled according to patent, and surface density is accordingly adjusted to match, and are made into 18650 batteries.
Take gained negative electrode tab (compacted density 1.55g/cm3) with mercury injection method porosity and tortuosity are tested, it makes a record.It will Pole piece does profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity (3 etc. divide thickness) with software statistics, makes a record.
After ready-made battery partial volume, calculates energy density (under the conditions of same shell), make a record.By resulting electricity Electric discharge recording capacity at multiplying power and -20 DEG C is tested in pond.
Performance detection
(1) pole piece porosity detects:
Test porosity: the open-cell porosity of the pole piece sample of above-described embodiment 1-8 preparation is tested using full-automatic mercury injection apparatus, most Big pressure is the porosity of the pole piece sample of 30000PSI and same procedure test comparison example 1 to comparative example 4.Characterization is through-hole Porosity, the pore volume ratio that can be directly connected to pole piece.
Calculate porosity: 1- expects that real density volume/porous electrode volume is surveyed, and porous electrode volume is dressing thickness * dressing The real density of area, material is calculated according to the real density of formula and respective material, obtains true solid body in porous electrode Product.Characterization is all porositys of pole piece (containing blind hole and closed pore).
Tortuosity, the length of the hole calculated by mercury injection withdrawal simulation are how many times of thickness.Exactly characterize For intercommunicating pore to the length of pole piece, length is shorter, illustrates that subsequent ionic conductance is better, closed pore is fewer, and surface holes are more.? Structural coefficient φ is in mercury injection method test the inside, characterizes true core and imaginary isometric and cross-section product parallel pipe column hollow billet Difference between beam model, its numerical value are the measurements for influencing the various factors of this difference.Structural coefficient indicates that fluid exists Seepage flow detour degree in hole, structural coefficient is bigger, and the degree that hole is bent detour is stronger.
Pole piece mercury injection method test result is shown in Table 1: test result is shown in Table 1:
According to table 1, the cathode compacted density of Examples 1 and 2 is in 1.68g/cm3And 1.6g/cm3, through-hole porosity is negative Compacted density 1.55g/cm of the pole between 27.2%-28.8%, with workshop normal process3Through-hole porosity 28.5%- 29.9%, difference is little, illustrates that pore-creating effect of the invention on cathode is obvious.
Calculate porosity is with the difference for testing through-hole porosity: embodiment 1-8 difference is about 2%-4%, comparison 1-7 difference Be 10.6%, 9.4%, 10.0%, 11.8%, 8.6%, 9.5%, 13.1%, illustrate comparative example have quite a few hole be mercury not into It goes, is exactly that some tortuosities are very high or the ratio of blind hole is very big.
Structural coefficient φ: embodiment it is universal all between 4-5, comparative example 1-7 is respectively as follows: 7.4,7.4,7.3,8.2, 6.7,6.6,8.6, illustrate that the mercury ejection of comparative example is slower, the big hole ratio of tortuosity is very high, and also side demonstrates pole piece Hole it is few, surface apertures are small.
(2) battery energy density
Battery prepared by the present invention is 18650 batteries, and the energy density of battery is compared using the battery of uniform size, Each embodiment and comparison energy density calculate table, are shown in Table 2 in detail:
The battery of embodiment 1 and embodiment 2 and comparative example 1,5,6,7 is that positive ternary mixes manganese, ratio as can be seen from Table 2 Identical anode, cathode are graphite, and cathode treatment process is different, embodiment 1,2 gravimetric energy densities be 186Wh/Kg and 183Wh/Kg, comparative example 1,5,6,7 are respectively 170Wh/Kg, 174Wh/Kg, 173Wh/Kg and 169Wh/Kg, illustrate the present invention Method obvious action played to energy density raising, comparison patent also has a certain upgrade, but space is little.
Embodiment 3, embodiment 4, embodiment 4, embodiment 6, from the point of view of embodiment 7, embodiment 8, respectively with comparative example 2,3,4 Compare, be generally higher than the energy density of 6%-9%, this still only handled one of them in positive and negative anodes as a result, if Positive and negative anodes are all made of this mode and handle, and energy density can also improve, and are calculated according to available data, compared with industry mainstream level It can be improved 12% or so.
The test of battery low temperature performance and the test of room temperature battery high rate performance under the conditions of (3) -20 DEG C.
The battery for preparing embodiment 1-8 and comparative example 1-7 at 25 DEG C of room temperature respectively with 0.5C constant-current constant-voltage charging extremely 3.65(ferric phosphate lithium cell)/4.2V(ternary and lithium manganate battery), 0.5C is discharged to after shelving under the conditions of -20 DEG C 48 hours 1.5V(ferric phosphate lithium cell)/2.5V(ternary and lithium manganate battery), discharge capacity is recorded, test result is shown in Table 3.
The battery for preparing embodiment 1-8 and comparative example 1-7 at 25 DEG C of room temperature respectively with 0.5C constant-current constant-voltage charging extremely 3.65 (ferric phosphate lithium cell)/4.2V (ternary and lithium manganate battery) are discharged to 2.0V shelving 0.5C/1C/3C after ten minutes (ferric phosphate lithium cell)/2.75V (ternary and lithium manganate battery) records discharge capacity, each embodiment and comparative example low temperature -20 At DEG C electric discharge and room temperature under different multiplying Discharge test be shown in Table 3:
Implementation 1 and embodiment 2 are phases in -20 DEG C of discharge capacitances directly compared with comparative example 1-7 as can be seen from Table 3 Poor obvious: Examples 1 and 2 conservation rate is 76%-79%, comparative example 1,5,6,7 be respectively 71%-72%, 74%-75%, 73%-74% and 68%-72% is not only conservation rate height, and consistency also increases, the consistency of comparative example 2 and 3 Also relatively high, relative low temperature capacity is also to have obvious promotion, illustrates that comparative example 2 and 3 also plays certain effect Fruit improves also than more significant battery performance.The corresponding comparative example 2,3,4 of the conservation rate of embodiment 3-8 is compared, higher In the case of energy density, the low temperature and high rate performance of battery improve 5%-10%, significant effect.Come from different multiplying electric discharge It sees, also similar with -20 DEG C of discharge capacitances, example scheme has clear improvement, it can be ensured that improve energy density situation Under have better multiplying power discharging property.
In summary: the present invention had not only been able to maintain pole piece high-pressure solid and has improved battery energy density, but also to improve battery pole piece equal Even property ensures the method for the performances such as multiplying power, circulation, low temperature.This method can guarantee to further increase pole piece compaction density situation Under, pole piece surface layer hole is uniform and quantity is more, closed pore and shrinkage cavity than regular meeting considerable decrease, improve the effective hole of pole piece Rate.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.

Claims (7)

1. a kind of secondary pore forming method of lithium ion battery, it is characterised in that: the following steps are included:
S1: pore creating material is heated to 40~120 DEG C, forms melt liquid；
S2: increasing melt liquid at the tail of coating machine and impregnate or spraying cabinet, and spray tank atomized inside pressure is 0.1~ 100KPa, atomization temperature are 60~130 DEG C, and soaking box is using 40~120 DEG C of melt liquid；
S3: prepared anode and cathode slurry is uniformly coated on collector substrate, after drying, with the speed of 0.01~5 meter per second Degree passes through soaking box, then cooling box by spray tank or with 1~60 m/min of speed, it is ensured that it is 1 that pole piece, which receives nebulisation time, ~300 seconds or soaking time 0.1~30 second, the cooler bin time, which is subject to, to be cooled to pore creating material and solidifies completely；
S4: the pole piece harvest coiled strip after pore creating material will be solidified, by roll squeezer according to normal flow roll-forming, maintaining roller pressure ring Border humid control is not within the scope of pore creating material absorbs water；
S5: the good pole piece of roll-in dries extractant by extraction box extraction time 1~300 second, then by oven, herein Band extractant condensing recovery is recycled；Or pole piece after roll-in is drenched into oven by hot wind wind, hot wind blows leaching treatment temperature 80 It~150 DEG C, handles the time 1~300 second, most of melting pore creating material liquid blowout is recycled, pole piece passes through high temperature nitrogen again The heat treatment of atmosphere oven, it is residual inside pore by being largely adsorbed onto depending on temperature is to correspond to high 5~10 DEG C of pore creating material boiling point Remaining pore creating material is evaporated by the mode of high-boiling, reduces residual to the greatest extent, allows pore creating material that can reach 99.9% or more It is recycled, oven band condensate recycling device, heat treatment time 1~30 minute；
S6: by ready-made pole piece, according to production procedure, process delivers production backward；
S7: taking that pole piece obtained by the 5th step is recorded as atomization respectively plus extraction is calculated as 1-1 and 1-2, atomization heat treatment be calculated as 1-3 and 1-4, impregnate plus extraction be calculated as 1-5 and 1-6, that impregnates heat treatment is calculated as 1-7 and 1-8, with mercury injection method test porosity and Tortuosity makes a record, and pole piece is done profile analysis, using low power SEM, analyzes upper, middle and lower layer porosity with software statistics, does Record easy to remember；
S8: respectively taking 2 for ready-made battery at random, is recorded as atomization respectively plus extraction is calculated as 1-1 and 1-2, atomization heat treatment It is calculated as 1-3 and 1-4, impregnates plus what is extracted is calculated as 1-5 and 1-6, that impregnates heat treatment is calculated as 1-7 and 1-8, after partial volume, meter Energy density is calculated, is made a record, by electric discharge recording capacity at resulting battery testing multiplying power and -20 DEG C.
2. a kind of secondary pore forming method of lithium ion battery according to claim 1, it is characterised in that: in the step S1 Pore creating material is in EC, DPC, paraffin, FEC, TCA, dibenzoic acid, Oxybenzone, tetracontane, 2- chlorobenzonitrile and 2,3-butanediol Any one.
3. a kind of secondary pore forming method of lithium ion battery according to claim 2, it is characterised in that: the EC, DPC, 2,3-butanediol and the corresponding extractant of tetracontane are respectively DMC, carbon disulfide, ethyl alcohol and dimethyl methyl acid amide.
4. a kind of secondary pore forming method of lithium ion battery according to claim 1, it is characterised in that: in the step S2 Spray tank atomized inside preferred pressure is 1~10KPa, is atomized 80~120 DEG C of preferable temperature, the melt liquid that soaking box uses Preferable temperature is 60~100 DEG C, and melt liquid viscosity is less than 100mPa*s.
5. a kind of secondary pore forming method of lithium ion battery according to claim 1, it is characterised in that: in the step S3 Receiving that the spraying preferred time is 5~180 seconds or soaking time is 0.5~5 second, the pole piece after immersion blows leaching with nitrogen, By the pore creating material melt of excess surface it is few as far as possible remain in pole piece, pole piece is sufficiently cooled to pore creating material and is solidified completely.
6. a kind of secondary pore forming method of lithium ion battery according to claim 1, it is characterised in that: in the step S4 Calendering carries out in roll squeezer, takes pole piece and facility environment moisture to control plus sternly to < 2%RH, rolling condition is 0.5-3.0 million Pa, the speed of calendering are 10~40m/min, form pole piece with a thickness of 90~190um, compacted density are as follows: graphite cathode 1.6~ 1.68g/cm3, positive 2.7~2.8g/cm of LiFePO43, positive 3.6~3.75g/cm of ternary3, positive LiMn2O4 3.1~ 3.2g/cm3。
7. a kind of secondary pore forming method of lithium ion battery according to claim 1, it is characterised in that: in the step S5 It is 10~120 seconds by the preferred time value that extraction box extracts, melt liquid viscosity that treated is less than 50mPa*S, processing It is preferred that the time is 10~180 seconds, oven band condensate recycling device, being heat-treated the preferred time is 3~20 minutes.
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