CN101436677B - Method for preparing battery - Google Patents
Method for preparing battery Download PDFInfo
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- CN101436677B CN101436677B CN200710165573XA CN200710165573A CN101436677B CN 101436677 B CN101436677 B CN 101436677B CN 200710165573X A CN200710165573X A CN 200710165573XA CN 200710165573 A CN200710165573 A CN 200710165573A CN 101436677 B CN101436677 B CN 101436677B
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- additive
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- current collector
- acid
- battery
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a method for preparing a battery, which comprises the following steps: a positive pole and a negative pole are prepared, a diaphragm is arranged between the positive pole and the negative pole, the positive pole comprises a positive current collector and a positive pole material loaded on the positive current collector, the negative pole comprises a negative current collector and a negative pole material loaded on the negative current collector, the diaphragm comprises a polymeric matrix, and the surface of at least one of the positive current collector, the negative current collector and the diaphragm is adhered with an additive, wherein a method for adhering the additive to the surface of at least one of the positive current collector, the negative current collector and the diaphragm comprises the following steps: the additive contacts the surface of at least one of the positive current collector, the negative current collector and the diaphragm in a gaseous form, and the temperature of the surface is lower than the gasification temperature of the additive during the contact. After the battery prepared by the method is circulated for 30 times, the residual rate of the capacity of the battery is between 93.7 and 96.9 percent.
Description
Technical field
The present invention relates to a kind of preparation method of battery.
Background technology
Portable electric appts is by leaps and bounds develops towards miniaturization and light-weighted direction along with mobile phone, notebook computer, PDA etc., requires to have higher capacity as the battery of its driving power.With the lithium rechargeable battery is the secondary cell of representative, good because of its energy density height, cycle performance, has a wide range of applications in field of portable electronic apparatus.
But, along with the difference of environment for use, various requirement has been proposed also for the performance of battery, such as emerging electric automobile, require battery can bear high current charge-discharge; Low temp area then requires battery to have good low temperature performance; Fail safe then is the necessary condition that all batteries all will possess.
Yet traditional secondary cell can only provide general performance, for improve battery in a certain respect or the performance of many aspects, usually need be by changing active material or adding additive and realize.Undoubtedly, add additive than changing the satisfied effect of the easier acquisition of active material, and cost and technical difficulty are all lower, are easy to realize industrialization production.
In general, add additive and mainly contain three kinds of methods: 1, add in the electrolyte; 2, when the collector batch mixing, add in the active material slurry; 3, form one deck additive layer on the surface of plus plate current-collecting body, negative current collector or barrier film, wherein, the 3rd kind of additive that method is added, the action effect of additive is the most remarkable.
According to prior art, form one deck additive layer at plus plate current-collecting body, negative current collector or membrane surface and mainly contain two kinds of methods, 1, directly in the method for plus plate current-collecting body, negative current collector or membrane surface coating one deck additive.Be difficult to control with this method coating layer thickness, it is excessive to apply easily, causes the adverse changes of battery capacity, and because be coated with excessive additive, has also correspondingly increased material cost; 2, add the method for one deck additive layer at plus plate current-collecting body, negative current collector or membrane surface by spray-on process (promptly spraying the suspension-turbid liquid method).But adopt this method in surface attachment the plus plate current-collecting body of additive, negative current collector or barrier film when preparing battery, the cycle performance of battery is relatively poor.
Summary of the invention
The objective of the invention is the relatively poor defective of cycle performance, a kind of cycle performance preparation method of battery preferably is provided for the battery that overcomes existing method preparation.
The invention provides a kind of preparation method of battery, this method comprises preparation positive pole and negative pole and barrier film is arranged between positive pole and the negative pole, described positive pole comprises plus plate current-collecting body and the positive electrode that loads on the plus plate current-collecting body, described negative pole comprises negative current collector and the negative material that loads on the negative current collector, described barrier film comprises polymeric matrix, and described plus plate current-collecting body, in negative current collector and the barrier film at least the surface attachment of one of them additive is arranged, wherein, make described additive be attached to described plus plate current-collecting body, in negative current collector and the barrier film at least the lip-deep method of one of them comprise and make the plus plate current-collecting body of described additive with gaseous form and battery, in negative current collector and the barrier film at least the surface of one of them contact, and the temperature on described surface is lower than the gasification temperature of additive during contact.
The present inventor is surprised to find that the relatively poor reason of cycle performance of the battery of existing spray-on process preparation is that the average grain diameter of the additive particulate that this method is adhered to is bigger on the surface of plus plate current-collecting body, negative current collector or barrier film; And in the process of preparation battery, promptly anodal, negative pole cut and anodal, negative pole and membrane coil around the time, additive comes off easily, thereby causes the effect of additive to weaken, therefore the cycle performance of the battery of preparation is relatively poor.And adopt the average grain diameter of additive particulate on surface of plus plate current-collecting body, negative current collector or barrier film of method of the present invention preparation less, and additive is not easy to come off, and therefore the cycle performance of the battery of preparation is better.
The battery that adopts existing spray-on process preparation is after 30 circulations, and the capacity surplus ratio of battery adopts method provided by the invention to prepare battery after 30 circulations at 72.6-77.6%, and the capacity surplus ratio of battery is at 93.7-96.9%.
Embodiment
Preparation method according to battery provided by the invention, this method comprises preparation positive pole and negative pole and barrier film is arranged between positive pole and the negative pole, described positive pole comprises plus plate current-collecting body and the positive electrode that loads on the plus plate current-collecting body, described negative pole comprises negative current collector and the negative material that loads on the negative current collector, described barrier film comprises polymeric matrix, and described plus plate current-collecting body, in negative current collector and the barrier film at least the surface attachment of one of them additive is arranged, wherein, make described additive be attached to described plus plate current-collecting body, in negative current collector and the barrier film at least the lip-deep method of one of them comprise and make the plus plate current-collecting body of described additive with gaseous form and battery, in negative current collector and the barrier film at least the surface of one of them contact, and the temperature on described surface is lower than the gasification temperature of additive during contact.
According to the present invention, the gasification temperature that the temperature on described surface is lower than additive during contact can make the additive of gaseous form undergo phase transition, and forms liquid or solid-state and is attached on the described surface, liquidly then can be changed into solid-state by further cooling.For the additives for battery of this area routine, general direct become by gaseous state solid-state.Experiment showed, that by this mode of the present invention, additive finally can form very tiny particle and be attached to very equably on the described surface.Although as long as when contact described surface the temperature gasification temperature that is lower than additive can realize purpose of the present invention, but under the preferable case, be attached on the described surface in order to make additive form solid particle fast, the temperature on described surface is lower than the curing temperature of additive during contact.For different additives, its curing temperature is different with gasification temperature, but experimental results show that, for this area additives for battery commonly used, curing temperature is generally than low 60-300 ℃ of gasification temperature, therefore, under the preferable case, the temperature on described surface is hanged down 60-300 ℃ than the gasification temperature of additive during contact." described surface " is meant in plus plate current-collecting body, negative current collector and the barrier film of desiring the battery contact with additive the surface of one of them at least herein.
Can obtain the gaseous form of additive by variety of way, for example, can be by described additive being heated to the gaseous form that obtains described additive under the gasification temperature that is not less than this additive.Described heating can be heating or decompression heating or inert gas shielding heating down down under the normal pressure.For the additive that chemical change takes place easily in high temperature or air ambient, preferably under reduced pressure or under inert gas shielding under heating or even the vacuum state electron beam heating obtain the gaseous form of this additive.
Described additive reacts only otherwise with the electrolyte of battery and gets final product, include but not limited to acid, strong acid weak base salt or acid anhydrides, described acid includes but not limited to one or more in ethanedioic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, phthalic acid, fumaric acid, acrylic acid and the methacrylic acid, and described strong acid weak base salt includes but not limited to NH
4Cl, described acid anhydrides includes but not limited to succinyl oxide and/or acetic anhydride.
Described additive is not had concrete restriction with the enforcement environment that described surface contacts, can not produce harmful effect collector (or barrier film) and the performance of additive own as long as guarantee the interpolation process of additive under this environment.Environmental factor comprises atmosphere atmosphere, air pressure, humidity, temperature etc.Generally speaking, the lithium rechargeable battery collector requires than higher ambient humidity, thereby the interpolation environmental requirement relative air humidity of additive is low; And the interpolation process need of additive heats up and undergoes phase transition, so thereby destroying the portions additive of the original performance of additive in this process, reacting with air, described additive contacts then with described surface and preferably realizes under inert gas shielding.
Among the present invention, described inert gas refers to not the gas that reacts with additive for example can be nitrogen, argon gas or air.
The present invention is not particularly limited with the degree that described surface contacts described additive, the amount that depends on required additive, usually, it is the 0.01-2 micron that the degree that described additive contacts with described surface makes the described thickness that is attached to the lip-deep additive of battery plus plate current-collecting body, negative current collector or barrier film, is preferably the 0.05-1.5 micron.The time of contact is depended on the gasification rate and the gasification distance of desired additives.When the gasification rate of the amount of desired additives and additive was determined, those skilled in the art's instruction according to the present invention was easy to determine the time of contact.For example, when the area on the surface of additive contact and the area of additive gasification equate, gasify apart from be 100-1000 millimeter, gasification rate be the 0.3-5 micron/minute and the thickness of desired additives when being the 0.05-1.5 micron, the time of contact can be 0.6-300 second.
According to the preparation method of battery of the present invention, this method comprises between preparation positive pole and negative pole and the positive pole and negative pole with the barrier film setting, constitutes the electrode group, and this electrode group is contained in the battery case, injects electrolyte, then battery case is sealed.
According to the present invention, described positive pole comprises plus plate current-collecting body and the positive electrode that loads on the plus plate current-collecting body, and described positive electrode contains positive active material, adhesive and conductive agent.
Described plus plate current-collecting body can be a various conducting base known in those skilled in the art, for example can be aluminium foil, Copper Foil, nickel plated steel strip or nickel screen.
Described positive active material can for example can be LiFePO 4, phosphoric acid vanadium lithium and LiCoO for well known to a person skilled in the art positive active material
2In one or more; Described adhesive can be for well known to a person skilled in the art various adhesives, for example can be in polytetrafluoroethylene, butadiene-styrene rubber, carboxymethyl cellulose (CMC), sodium carboxymethylcellulose, hydroxypropyl methylcellulose, POLYPROPYLENE GLYCOL and the Kynoar one or more, the content of described adhesive is the 0.08-8 weight % of positive active material, is preferably 1-5 weight %; Described conductive agent can be for well known to a person skilled in the art various conductive agents, for example can be in carbon black, acetylene black, nickel powder, copper powder, cobalt hydroxide, cobalt oxide and the electrically conductive graphite one or more, the consumption of described conductive agent can be preferably 1-10 weight % for the 1-15 weight % of positive active material.
According to the present invention, described negative pole comprises negative current collector and the negative material that loads on the negative current collector, and described negative material contains negative electrode active material, adhesive and conductive agent.
Described negative current collector can be various collectors conventionally known to one of skill in the art, for example can be aluminium foil, Copper Foil, nickel plating perforated steel ribbon or silicon thin film.
Described negative electrode active material is conventionally known to one of skill in the art, can be for being the negative electrode active material of routine of the secondary cell of positive active material with the nickel hydroxide, and for example, for the nickle-hydrogen alkaline secondary cell, negative electrode active material can be hydrogen bearing alloy; For the NI-G alkaline secondary cell, negative electrode active material can be CdO; For lithium rechargeable battery, negative electrode active material can be graphite.
The adhesive of described negative pole is conventionally known to one of skill in the art, for example can be selected from polyvinyl alcohol, polytetrafluoroethylene (PTFE), CMC (CMC), butadiene-styrene rubber (SBR) and the Kynoar one or more.In general, the content of described adhesive is the 0.5-8 weight % of negative electrode active material, is preferably 2-5 weight %.
Described cathode conductive agent can be for well known to a person skilled in the art various conductive agents, for example can be in carbon black, acetylene black, nickel powder, copper powder, cobalt hydroxide, cobalt oxide and the electrically conductive graphite one or more, the consumption of described conductive agent can be preferably 1-10 weight % for the 1-15 weight % of positive active material.
The solvent that is used to prepare anode sizing agent and cathode size of the present invention can be selected from conventional solvent, includes but not limited in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols one or more.The consumption of solvent can be coated on the described conducting base described slurry and gets final product.In general, the consumption of solvent is that to make the concentration of active material in the slurries be 40-90 weight %, is preferably 50-85 weight %.
The same with prior art, the preparation method of described positive pole is included in and applies the slurry that contains positive active material, adhesive and conductive agent on the plus plate current-collecting body, gets final product anodally after drying, roll-in, the section.Described drying is usually at 50-160 ℃, carries out under preferred 80-150 ℃.
The preparation method of negative pole is identical with anodal preparation method, just replaces containing the slurry of positive active material, adhesive and conductive agent with the slurry that contains negative electrode active material and adhesive.
According to the present invention, described barrier film comprises polymeric matrix, such as being composite membrane, polyethylene/polypropylene/polyethylene composite film (PE/PP/PE film) or the polypropylene screen that is formed through welding or bonding in the modified poly ethylene felt of respectively producing the trade mark, modified polypropene felt, ultra-fine fibre glass felt, vinylon felt, nylon felt and the wettability microporous polyolefin film of known each manufacturer production by those skilled in the art.
Below will the present invention will be further described by specific embodiment.
Embodiment 1
This embodiment illustrates the preparation method of battery provided by the invention.
1, Zheng Ji preparation
It is 500 millimeters that 10 gram succinyl oxides are placed a bottom surface length, wide is 50 millimeters, height is in 110 millimeters the container, be heated to 120 ℃ of the fusing points of succinyl oxide, and continue to heat, temperature is controlled near 261 ℃ of the boiling points of succinyl oxide, the succinyl oxide start vaporizer, the lithium ion battery aluminium foil plus plate current-collecting body that gasification temperature than succinyl oxide is hanged down 200 ℃ 20 micron thickness lies in a horizontal plane on the beaker mouth, the plus plate current-collecting body size can cover the beaker mouth fully, succinyl oxide all evaporates after 50 seconds, collector is lifted down, obtained the plus plate current-collecting body of surface attachment succinyl oxide.With the ESEM instrument detecting collector cross section of Japanese JEOL company, find that the thickness of aluminium foil anode collection surface succinyl oxide is 0.1 micron.Adopt the additive of this plus plate current-collecting body surface attachment of DM2000 type metallography microscope sem observation of Switzerland Lycra company production, observing additive is discontinuous distribution, a lot of granules are evenly distributed on the surface of plus plate current-collecting body, and the average grain diameter of additive particulate is 50 microns.
Respectively with 100 gram positive active material LiFePO
4, 5 gram binding agent Kynoar (PVDF) and 5 gram conductive agent acetylene blacks join in the 50 gram N-methyl pyrrolidones, stir the uniform anode sizing agent of formation then in de-airing mixer.
This anode sizing agent is coated on the both sides of the plus plate current-collecting body of the above-mentioned surface attachment succinyl oxide that obtains equably, 150 ℃ of following oven dry, roll-ins then, cuts to make and be of a size of 44 * 485 millimeters positive pole, wherein contain the 8.3 gram active component LiFePO that have an appointment
4
2, the preparation of negative pole
100 gram negative electrode active composition native graphites, 5 gram bonding agent Kynoar, 5 gram conductive agent carbon blacks are joined in the 50 gram N-methyl pyrrolidones, in de-airing mixer, stir then and form uniform cathode size.
This cathode size is coated on the both sides that thickness is 12 microns Copper Foil equably, then in 90 ℃ of following oven dry, roll-in, cut to make and be of a size of 45 * 480 millimeters negative pole, wherein contain the 3.8 gram active component native graphites of having an appointment.
3, the assembling of battery
Respectively above-mentioned positive pole, negative pole and polypropylene screen are wound into the pole piece of a square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in EC/EMC/DEC=1: form nonaqueous electrolytic solution in 1: 1 the mixed solvent, this electrolyte is injected the battery aluminum hull with the amount of 3.8g/Ah, battery A1 is made in sealing.
Above-mentioned positive pole cut and anodal, negative pole and membrane coil around the time, do not find the coming off of additive of anodal surface attachment.
Embodiment 2
This embodiment illustrates the preparation method of battery provided by the invention.
1, Zheng Ji preparation
Respectively with 100 gram positive active material LiFePO
4, 5 gram binding agent Kynoar (PVDF) and 5 gram conductive agent acetylene blacks join in the 50 gram N-methyl pyrrolidones, stir the uniform anode sizing agent of formation then in de-airing mixer.
This anode sizing agent is coated on the both sides that thickness is 20 microns aluminium foil equably, 150 ℃ of following oven dry, roll-ins then, cuts to make and be of a size of 44 * 485 millimeters positive pole, wherein contain the 8.3 gram active component LiFePO that have an appointment
4
2, the preparation of negative pole
With 10 gram succinyl oxides place a bottom surface length be 500 millimeters, wide be that 50 millimeters, height are in 110 millimeters the container, be heated near 261 ℃ of the boiling points of succinyl oxide, the succinyl oxide start vaporizer, is the thickness than low 230 ℃ of the gasification temperature of succinyl oxide that 20 microns lithium ion battery silicon film cathode collector is placed on the beaker mouth, silicon thin film negative current collector size can cover the beaker mouth fully, succinyl oxide all evaporates after 30 seconds, collector is lifted down, obtained the silicon thin film negative current collector of surface attachment succinyl oxide.With the ESEM instrument detecting collector cross section of Japanese JEOL company, find that the thickness of the succinyl oxide of silicon thin film negative pole currect collecting surface is 0.15 micron.Adopt the additive of this negative current collector surface attachment of DM2000 type metallography microscope sem observation of Switzerland Lycra company production, observing additive is discontinuous distribution, a lot of granules are evenly distributed on the surface of negative current collector, and the average grain diameter of additive particulate is 10 microns.
100 gram negative electrode active composition native graphites, 5 gram bonding agent Kynoar, 5 gram conductive agent carbon blacks are joined in the 50 gram N-methyl pyrrolidones, in de-airing mixer, stir then and form uniform cathode size.
This cathode size is coated on equably the both sides of silicon thin film negative current collector of the surface attachment succinyl oxide of above-mentioned preparation, then in 90 ℃ of following oven dry, roll-in, cut to make and be of a size of 45 * 480 millimeters negative pole, wherein contain the 3.8 gram active component native graphites of having an appointment.
3, the assembling of battery
Respectively above-mentioned positive pole, negative pole and polypropylene screen are wound into the pole piece of a square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in EC/EMC/DEC=1: form nonaqueous electrolytic solution in 1: 1 the mixed solvent, this electrolyte is injected the battery aluminum hull with the amount of 3.8g/Ah, battery A2 is made in sealing.
Above-mentioned negative pole cut and anodal, negative pole and membrane coil around the time, do not find coming off of additive that negative terminal surface is adhered to.
Embodiment 3
This embodiment illustrates the preparation method of battery provided by the invention.
1, Zheng Ji preparation
Respectively with 100 gram positive active material LiFePO
4, 5 gram binding agent Kynoar (PVDF) and 5 gram conductive agent acetylene blacks join in the 50 gram N-methyl pyrrolidones, stir the uniform anode sizing agent of formation then in de-airing mixer.
This anode sizing agent is coated on the both sides that thickness is 20 microns aluminium foil equably, 150 ℃ of following oven dry, roll-ins then, cuts to make and be of a size of 44 * 485 millimeters positive pole, wherein contain the 8.3 gram active component LiFePO that have an appointment
4
2, the preparation of negative pole
100 gram negative electrode active composition native graphites, 5 gram bonding agent Kynoar, 5 gram conductive agent carbon blacks are joined in the 50 gram N-methyl pyrrolidones, in de-airing mixer, stir then and form uniform cathode size.
This cathode size is coated on the both sides that thickness is 12 microns Copper Foil equably, then in 90 ℃ of following oven dry, roll-in, cut to make and be of a size of 45 * 480 millimeters negative pole, wherein contain the 3.8 gram active component native graphites of having an appointment.
3, the preparation of barrier film
With 10 gram methacrylic acids place a bottom surface length be 500 millimeters, wide be that 50 millimeters, height are in 110 millimeters the container, be heated to 72 ℃ of the fusing points of methacrylic acid, and continue to heat, the methacrylic acid start vaporizer, lithium ion battery PE/PP/PE barrier film than low 50 ℃ of the gasification temperature of methacrylic acid is placed on the beaker mouth, the barrier film size can cover the beaker mouth fully, methacrylic acid all evaporates after 120 seconds, barrier film is lifted down, obtained the PE/PP/PE barrier film of surface attachment methacrylic acid.With the ESEM instrument detecting collector cross section of Japanese JEOL company, find that the thickness of the methacrylic acid of PE/PP/PE membrane surface is 1.5 microns.The additive that this membrane surface of DM2000 type metallography microscope sem observation that adopts Switzerland Lycra company to produce adheres to, observing additive is discontinuous distribution, and a lot of granules are evenly distributed on the surface of barrier film, and the average grain diameter of additive particulate is 5 microns.
4, the preparation of battery
Respectively with the pole piece of the square lithium ion battery of PE/PP/PE membrane coil coiled of above-mentioned positive pole, negative pole and surface attachment methacrylic acid, subsequently with LiPF
6Concentration by 1 mol is dissolved in EC/EMC/DEC=1: form nonaqueous electrolytic solution in 1: 1 the mixed solvent, this electrolyte is injected the battery aluminum hull with the amount of 3.8g/Ah, battery A3 is made in sealing.
Above-mentioned positive pole, negative pole and membrane coil around the time, do not find coming off of additive that membrane surface adheres to.
Comparative Examples 1
This Comparative Examples illustrates the preparation method of existing battery.
The method identical with embodiment 1 prepares battery AC1, and different is to prepare the plus plate current-collecting body of surface attachment succinyl oxide according to the methods below.
10 gram succinyl oxides were ground in agate mortar 5 minutes, until all becoming very thin powder.Pulverous succinyl oxide is placed 50 ml beakers, the absolute ethyl alcohol that adds 15 milliliters, stirring makes it to form uniformly outstanding thick liquid, then suspension-turbid liquid is packed in the wounded in the battle spray bottle that spills shower nozzle, suspension-turbid liquid is sprayed onto on the lithium ion battery aluminium foil plus plate current-collecting body of 20 micron thickness equably with the spray bottle.Spray back collector is put in 50 ℃ of baking ovens and dried, obtained the plus plate current-collecting body of surface attachment succinyl oxide.With the ESEM instrument detecting collector cross section of Japanese JEOL company, find that the thickness of aluminium foil anode collection surface succinyl oxide is 2 microns.Adopt the additive of this plus plate current-collecting body surface attachment of DM2000 type metallography microscope sem observation of Switzerland Lycra company production, observing additive is discontinuous distribution, a lot of granules are uneven distribution on the anode collection surface, the average grain diameter of additive particulate is 800 microns.
In the preparation process of this battery, promptly positive pole cut and anodal, negative pole and membrane coil around the time, the additive of finding anodal surface attachment has significantly and comes off.
Comparative Examples 2
This Comparative Examples illustrates the preparation method of existing battery.
The method identical with embodiment 2 prepares battery AC2, and different is to prepare the negative current collector of surface attachment succinyl oxide according to the methods below.
10 gram succinyl oxides were ground in agate mortar 5 minutes, until all becoming very thin powder.Pulverous succinyl oxide is placed 50 ml beakers, the absolute ethyl alcohol that adds 15 milliliters, stirring makes it to form uniformly outstanding thick liquid, then suspension-turbid liquid is packed in the wounded in the battle spray bottle that spills shower nozzle, suspension-turbid liquid is sprayed onto on the lithium ion battery silicon film cathode collector of 12 micron thickness equably with the spray bottle.Spray back collector is put in 50 ℃ of baking ovens and dried, obtained the negative current collector of surface attachment succinyl oxide.With the ESEM instrument detecting collector cross section of Japanese JEOL company, find that the thickness of silicon thin film negative pole currect collecting surface succinyl oxide is 1.5 microns.Adopt the additive of this negative current collector surface attachment of DM2000 type metallography microscope sem observation of Switzerland Lycra company production, observing additive is discontinuous distribution, a lot of granules are uneven distribution on the negative pole currect collecting surface, the average grain diameter of additive particulate is 600 microns.
In the preparation process of this battery, promptly negative pole cut and anodal, negative pole and membrane coil around the time, the additive that the discovery negative terminal surface is adhered to has significantly and comes off.
Comparative Examples 3
This Comparative Examples illustrates the preparation method of existing battery.
The method identical with embodiment 3 prepares battery AC3, and different is to prepare the barrier film of surface attachment methacrylic acid according to the methods below.
10 gram methacrylic acids were ground in agate mortar 5 minutes, until all becoming very thin powder.Pulverous methacrylic acid is placed 50 ml beakers, the absolute ethyl alcohol that adds 15 milliliters, stirring makes it to form the outstanding thick liquid of uniform methacrylic acid dissolving supersaturation, then suspension-turbid liquid is packed in the wounded in the battle spray bottle that spills shower nozzle, suspension-turbid liquid is sprayed onto on the lithium ion battery PE/PP/PE barrier film of methacrylic acid micron thickness equably with the spray bottle.Spray back barrier film is put in 50 ℃ of baking ovens and dried, obtained the barrier film of surface attachment methacrylic acid.With the ESEM instrument detecting barrier film cross section of Japanese JEOL company, find that the thickness of PE/PP/PE membrane surface methacrylic acid is 1.2 microns.The additive that this membrane surface of DM2000 type metallography microscope sem observation that adopts Switzerland Lycra company to produce adheres to, observing additive is discontinuous distribution, and a lot of granules are uneven distribution on membrane surface, and the average grain diameter of additive particulate is 1000 microns.
In the preparation process of this battery, promptly anodal, negative pole and membrane coil around the time, the additive that the discovery membrane surface adheres to has significantly and comes off.
Embodiment 4-6
This embodiment illustrates the cycle performance of the battery of embodiment 1-3 preparation.
Under normal temperature, relative humidity 25-85% environmental condition, respectively measure battery A1, A2 that the foregoing description 1-3 makes and the cycle performance of A3.Assay method is as follows:
At first, use BS-9300 (R) secondary cell device for detecting performance, electric current with 200 milliamperes (0.2C) charges to 3.8 volts to mesuring battary, shelved 5 minutes, be discharged to 2.5 volts in order to 1000 milliamperes (1C) then, shelved again 5 minutes, with 200 milliamperes of (0.2C) constant current charge to 4.2 volts, 20 milliamperes of charging cut-off currents.Be discharged to 2.5 volts with 200 milliamperes then, measure the initial capacity that obtains battery discharge.Circulation repeats with 200 milliamperes of (0.2C) constant current charge to 4.2 volts; Be discharged to 2.5 volts charge and discharge process with 200 milliamperes (0.2C) again, write down the loop ends capacity of the 1st time and the 30th time, and be calculated as follows the battery capacity surplus ratio:
Capacity surplus ratio=loop ends capacity/initial capacity * 100%.
Measurement result is as shown in table 1 below.
Comparative Examples 4-6
The performance of the battery of this Comparative Examples explanation Comparative Examples 1-3 preparation.
According to the method identical battery AC1, AC2 and the AC3 that Comparative Examples 4-6 prepares carried out the cycle performance test with embodiment 4-6.Measurement result is as shown in table 1 below.
Table 1
| Embodiment or Comparative Examples | Battery | The 1st cyclic discharge capacity (milliampere-hour) | The 30th cyclic discharge capacity (milliampere-hour) | 30 circulation back capacity surplus ratios (%) |
| Embodiment 4 | A1 | 1030 | 965 | 93.7％ |
| Embodiment 5 | A2 | 1009 | 978 | 96.9％ |
| Embodiment 6 | A3 | 1023 | 960 | 93.8％ |
| Comparative Examples 4 | AC1 | 1008 | 782 | 77.6％ |
| Comparative Examples 5 | AC2 | 1020 | 751 | 73.6％ |
| Comparative Examples 6 | AC3 | 1008 | 732 | 72.6％ |
From the result shown in the table 1 as can be seen, the battery that adopts existing method preparation is after 30 circulations, the capacity surplus ratio of battery adopts method provided by the invention to prepare battery after 30 circulations at 72.6-77.6%, and the capacity surplus ratio of battery is at 93.7-96.9%.Therefore, compare, adopt the battery of method preparation provided by the invention to have better cycle performance with existing method.
Claims (8)
1. the preparation method of a battery, this method comprises preparation positive pole and negative pole and barrier film is arranged between positive pole and the negative pole, described positive pole comprises plus plate current-collecting body and the positive electrode that loads on the plus plate current-collecting body, described negative pole comprises negative current collector and the negative material that loads on the negative current collector, described barrier film comprises polymeric matrix, and described plus plate current-collecting body, in negative current collector and the barrier film at least the surface attachment of one of them additive is arranged, it is characterized in that, make described additive be attached to described plus plate current-collecting body, in negative current collector and the barrier film at least the lip-deep method of one of them comprise and make the plus plate current-collecting body of described additive with gaseous form and battery, in negative current collector and the barrier film at least the surface of one of them contact, and the temperature on described surface is lower than the gasification temperature of additive during contact, and described additive can be with the plus plate current-collecting body of gaseous form and battery, in negative current collector and the barrier film at least the surface of one of them contact.
2. method according to claim 1, wherein, the temperature on described surface is hanged down 60-300 ℃ than the gasification temperature of additive during contact.
3. method according to claim 1, wherein, by described additive being heated to the gaseous form that obtains described additive under the gasification temperature that is not less than this additive.
4. method according to claim 1 wherein, describedly is attached in plus plate current-collecting body, negative current collector and the barrier film at least that the thickness of the lip-deep additive of one of them is the 0.01-2 micron.
5. according to any described method among the claim 1-4, wherein, described additive is ethanedioic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, phthalic acid, fumaric acid, acrylic acid, methacrylic acid, NH
4In Cl, succinyl oxide and the acetic anhydride one or more.
6. method according to claim 1, wherein, described plus plate current-collecting body is aluminium foil, Copper Foil, nickel plated steel strip or nickel screen, and described positive electrode contains positive active material, adhesive and conductive agent, and described positive active material is LiFePO 4, phosphoric acid vanadium lithium and LiCoO
2In one or more, described adhesive is one or more in polytetrafluoroethylene, butadiene-styrene rubber, carboxymethyl cellulose, sodium carboxymethylcellulose, hydroxypropyl methylcellulose, POLYPROPYLENE GLYCOL and the Kynoar, and described conductive agent is one or more in carbon black, acetylene black, nickel powder, copper powder, cobalt hydroxide, cobalt oxide and the electrically conductive graphite.
7. method according to claim 1, wherein, described negative current collector is aluminium foil, Copper Foil, nickel plating perforated steel ribbon or silicon thin film, described negative material contains negative electrode active material, adhesive and conductive agent, described negative electrode active material is hydrogen bearing alloy, CdO or graphite, described adhesive is one or more in polyvinyl alcohol, polytetrafluoroethylene, CMC, butadiene-styrene rubber and the Kynoar, and described conductive agent is one or more in carbon black, acetylene black, nickel powder, copper powder, cobalt hydroxide, cobalt oxide and the electrically conductive graphite.
8. method according to claim 1, wherein, described barrier film is composite membrane, polyethylene/polypropylene/polyethylene composite film or the polypropylene screen of modified poly ethylene felt, modified polypropene felt, ultra-fine fibre glass felt, vinylon felt, nylon felt and wettability microporous polyolefin film.
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| CN101752563B (en) * | 2010-01-08 | 2012-09-05 | 惠州市赛能电池有限公司 | Lithium ion battery anode material and preparation method thereof |
| JP5534369B2 (en) * | 2010-02-22 | 2014-06-25 | トヨタ自動車株式会社 | Lithium ion secondary battery, its manufacturing method and vehicle |
| CN103840142B (en) * | 2014-03-06 | 2016-08-24 | 成羽 | The manufacture method of nickel copper-clad composite and application, accumulator, spark plug |
| CN103928659B (en) * | 2014-04-26 | 2015-12-09 | 常州大学 | A kind of rechargeable battery |
| CN104577089A (en) * | 2014-11-19 | 2015-04-29 | 山东精工电子科技有限公司 | Preparation method of lithium titanate negative-electrode slurry |
| CN107710452A (en) * | 2015-06-25 | 2018-02-16 | 日本高度纸工业株式会社 | Battery separator, secondary cell |
| JP6946295B2 (en) * | 2016-07-28 | 2021-10-06 | 三洋電機株式会社 | How to manufacture a secondary battery |
| CN111834667A (en) * | 2019-04-16 | 2020-10-27 | 深圳新宙邦科技股份有限公司 | Preparation method of polymer electrolyte membrane |
| CN112652801B (en) * | 2020-12-23 | 2022-03-18 | 深圳市言九电子科技有限公司 | Button battery roll core, preparation method thereof and button battery using same |
| WO2024090206A1 (en) * | 2022-10-25 | 2024-05-02 | パナソニックＩｐマネジメント株式会社 | Negative electrode for secondary battery, and secondary battery |
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| CN1335652A (en) * | 2000-07-25 | 2002-02-13 | 三星Sdi株式会社 | Electrolyte for lithium sulphur cell and lithium sulphur cell containing the same electrolyte |
| EP1458048A1 (en) * | 2003-03-13 | 2004-09-15 | Samsung SDI Co., Ltd. | A non-aqueous electrolyte and a lithium secondary battery comprising the same |
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| CN1335652A (en) * | 2000-07-25 | 2002-02-13 | 三星Sdi株式会社 | Electrolyte for lithium sulphur cell and lithium sulphur cell containing the same electrolyte |
| EP1458048A1 (en) * | 2003-03-13 | 2004-09-15 | Samsung SDI Co., Ltd. | A non-aqueous electrolyte and a lithium secondary battery comprising the same |
| CN1540794A (en) * | 2003-04-03 | 2004-10-27 | 三星Sdi株式会社 | Nonquueous electrolyte and lithium secondary battery includng same |
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