CN101651227A - High lifetime water-soluble lithium battery and preparation process thereof - Google Patents
High lifetime water-soluble lithium battery and preparation process thereof Download PDFInfo
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- CN101651227A CN101651227A CN200910018152A CN200910018152A CN101651227A CN 101651227 A CN101651227 A CN 101651227A CN 200910018152 A CN200910018152 A CN 200910018152A CN 200910018152 A CN200910018152 A CN 200910018152A CN 101651227 A CN101651227 A CN 101651227A
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Abstract
The invention relates to a high lifetime water-soluble lithium battery and preparation process thereof. The raw materials of the anode comprise the following components by weight percent: 2.2-5.8% ofwaterborne adhesive, 56%-65% of electroactive material LiFePO4, 2.3%-4.7% of conductive carbon black and 31-35.5% of deionized water and the viscosity is controlled to 1800-3200mPa-s. The process is that deionized water and waterborne adhesive are stirred in low speed for 5-10min, the rotate speed is 5-10Hz, then the mixture is mixed in high speed for 45-60min, the rotate speed is 30-45Hz, then electroactive material LiFePO4 and conductive carbon black are added to vacuumize and then stir for 4-6h in high speed, the vacuum value is not more than -0.095MPa, the rotate speed is 30-45Hz, and finally the high lifetime water-soluble lithium battery anode slurry can be obtained. The anode of the invention uses waterborne adhesive instead of traditional N-methylpyrrolidone and the anode slurry prepared from waterborne adhesive is adopted for coating so as to be environmentally friendly, increase the battery cycle life and reduce raw material cost by 20-30%. The cathode adopts mesophase carbonmicrospheres instead of the traditional cathode material so as to improve the extraction property of lithium ions in the cathode and increase the battery cycle life.
Description
Technical field
The present invention relates to a kind of lithium rechargeable battery (group) and manufacture craft thereof, relate in particular to a kind of high lifetime water-soluble lithium battery and manufacture craft thereof.
Background technology
At present, domestic most of producer uses oiliness system polyvinylidene fluoride/N-methyl pyrrolidone (PVDF/NMP) to produce LiFePO4 (LiFePO
4) lithium rechargeable battery, cost is high and environment had pollution.
The patent No. is CN200510111791.6, denomination of invention is " a kind of preparation method of lithium ion battery anode material lithium iron phosphate ", Granted publication number is CN100420075, Granted publication day is: the patent of 2008.09.17, a kind of preparation method of lithium ion battery anode material lithium iron phosphate is disclosed, its preparation method is as follows: with trivalent iron salt, lithium salts, phosphate and ascorbic acid are mixed in the solvent and react, iron in the trivalent iron salt wherein, lithium in the lithium salts, the phosphorus in the phosphate and the mol ratio of ascorbic acid are 1: 0.95～1.05: 1: 0.25～2, the concentration of iron in the molysite in solvent is 0.1～2mol/L, reacted 0.5～30 hour, 60～100 ℃ of following solvent flashings also wash resultant unbodied LiFePO4 precipitation, unbodied LiFePO4 is deposited in nitrogen or argon gas or the gaseous mixture atmosphere then, be warming up to 450～800 ℃ with 5～30 ℃/min rate of heat addition, constant temperature calcining 20～600min, be cooled to room temperature with 1～20 ℃/min rate of temperature fall then, make the lithium ion battery anode material lithium iron phosphate of crystal formation.
Number of patent application is that CN200610122368.0, denomination of invention are the patent of " high-powered lithium ferric phosphate dynamic battery and manufacture craft thereof ", discloses a kind of high-powered lithium ferric phosphate dynamic battery and manufacture craft thereof, and its claim is:
" 1, a kind of high-powered lithium ferric phosphate dynamic battery; it comprises housing, positive plate, negative plate, barrier film, electrolyte; wherein positive plate and negative plate are made up of the positive and negative electrode collector of same size and the active material that is coated on the positive and negative electrode collector respectively; it is characterized in that the plus plate current-collecting body employing tiltedly draws the aluminium net, conductive agent is selected carbon black, graphite, nanometer Al for use
2O
3, nanometer Ag, nanometer SiO
2In one or more mixtures, the positive electrode binding agent is selected one or more mixtures in acrylic acid-styrene polymer, acrylic acid-silicon-oxygen polymer, cinnamic acrylic ester polymer, styrene-butadiene polymer, butadiene-acrylonitrile polymer or the acrylic polymer for use, and positive electrode is selected the LiFePO4 Li1-xMxFePO that adopts through ion doping for use
4, M is Co, Mn, Mg, Cr, Ti, Mo, Nd, Ni one of them, 0≤X≤0.1.
2, high-powered lithium ferric phosphate dynamic battery according to claim 1 is characterized in that the percentage by weight proportioning of anode sizing agent: positive electrode 67%～90%; Conductive agent 0%～13%; Acrylic polymer 5%～10%, the percentage by weight proportioning of cathode size: negative material 85%～96%; Conductive agent 1%～5%; Sodium carboxymethylcellulose 2～5%; Butadiene-styrene rubber 1%～5%.
3, high-powered lithium ferric phosphate dynamic battery according to claim 1 is characterized in that battery cathode sheet comprises graphite, conductive agent and negative pole metal collector, and negative material is selected native graphite for use, MCMB, one or more mixtures in the polymer charcoal.
4, high-powered lithium ferric phosphate dynamic battery according to claim 1, it is characterized in that the battery cathode conductive agent selects one or more mixtures in carbon black, the graphite for use, the negative material binding agent is selected one or more mixtures in sodium carboxymethylcellulose, the butadiene-styrene rubber binding agent for use.
5, high-powered lithium ferric phosphate dynamic battery according to claim 1, it is characterized in that plus plate current-collecting body is tiltedly to draw the aluminium net, be by aluminum steel be compiled into be parallel to each other intersect tiltedly draw in the net thickness 0.10～0.15mm, percent opening 20～40 holes/cm2, aperture 0.2～0.5mm that net forms.
6, a kind of high-powered lithium ferric phosphate dynamic battery manufacture craft, after the aqueous solution form slurry of positive electrode, conductive agent and acrylic polymer binder, on metal collector, apply, after 80～150 ℃ of following dryings, forming thickness after roll-in is the pole piece of 150～250 μ, and its compacted density is 1.8～2.5g/cm
3Above-mentioned positive plate contacts with the block of battery, the aqueous solution form slurry of negative material, conductive agent and sodium carboxymethylcellulose, butadiene-styrene rubber binding agent, on metal collector, be coated with, after 80～150 ℃ of following dryings, forming thickness after roll-in is the pole piece of 80～160 μ, its compacted density 1.3～1.8g/cm
3Above-mentioned pole piece contacts with battery container, battery cathode, barrier film and positive pole are reeled to superimposition, make the helical form battery, the helical form battery is inserted battery container, insulation board places the upper and lower surface of helical form battery, and anodal aluminium pole ears contacts with battery cap, and negative pole nickel lug contacts with battery container.Inject electrolyte solution in battery container, promptly get high-powered lithium ferric phosphate dynamic battery behind the forming and capacity dividing, it is characterized in that plus plate current-collecting body adopts tiltedly to draw the aluminium net, conductive agent is selected carbon black, graphite, nanometer Al for use
2O
3, nanometer Ag, nanometer SiO
2In one or more mixtures, the positive electrode binding agent is selected one or more mixtures in acrylic acid-styrene polymer, acrylic acid-silicon-oxygen polymer, cinnamic acrylic ester polymer, styrene-butadiene polymer, butadiene-acrylonitrile polymer or the acrylic polymer for use, and positive electrode adopts the LiFePO4 Li1-xMxFePO through ion doping
4, M is Co, Mn, Mg, Cr, Ti, Mo, Nd, Ni one of them, 0≤X≤0.1.
7, high-powered lithium ferric phosphate dynamic battery manufacture craft according to claim 6 is characterized in that the percentage by weight proportioning of anode sizing agent: positive electrode 67%～90%; Conductive agent 0%～13%; Acrylic polymer 5%～10%; The percentage by weight proportioning of cathode size: negative material 85%～96%; Conductive agent 1%～5%; Sodium carboxymethylcellulose 2～5%; Butadiene-styrene rubber 1%～5%.
8, high-powered lithium ferric phosphate dynamic battery manufacture craft according to claim 6, after it is characterized in that positive electrode, binding agent acrylic copolymer and conductive agent mixed slurry, vertical two-sided blade coating on metal collector, coating temperature is 100～150 ℃, coating speed: 2～5 meters/minute, after the drying, forming thickness after roll-in is the pole piece of 150～250 μ, and its compacted density is 1.8～2.5g/cm
3”
The patent No. is CN200710058352.2, Granted publication number is CN100522803C, Granted publication day is 2009.08.05, denomination of invention is the patent of " a kind of hydrothermal synthesis method of lithium ion battery anode material lithium iron phosphate ", a kind of hydrothermal synthesis method of lithium ion battery anode material lithium iron phosphate is disclosed, it is characterized by and may further comprise the steps: the first step, hydrothermal synthesis reaction is with the lithium source and the phosphorus source is water-soluble or with after water mixes, add in the autoclave, add quaternary cationic surfactant and APES class non-ionic surface active agent then, behind the air in the dead volume in the inert gas purge still, sealing autoclave, be heated to 40～50 ℃ under stirring, open inlet valve and vent valve, add pure divalent iron salt solution again, sealing autoclave then, in 140～180 ℃, reacted 30～480 minutes, this moment, corresponding self-generated pressure was 0.36～1.0MPa, the control of charging technology parameter is implemented in reaction, the proportioning that promptly adds material is controlled to be: Li: Fe: the P mol ratio is 3.0～3.15: 1: 1.0～1.15, when beginning to react, reactant concentration is counted 0.4～0.5mol/L with ferrous ion concentration, the concentration of quaternary cationic surfactant is 0.2～2g/L, and the concentration of APES class non-ionic surface active agent is 0.05～0.1g/L; Second step, after the filtration of product, washing and dry above-mentioned reaction are finished, autoclave cools off fast by cooling water, open bleeder valve, product is filtered and washs to the acid ion that does not have divalent iron salt, obtain filter cake and mother liquor, filter cake obtains canescence LiFePO in 60 ℃～120 ℃ vacuumizes 1～2 hour
4Powder; In the 3rd step, carbon coat to be handled the product of the second step gained and water dissolvable carbon containing organic compound 100: 10～20 mixings of pressing mass ratio, under inert gas shielding, in 600 ℃ of roastings 2～3 hours, obtains the LiFePO4 of carbon coating.
The patent No. be CN200510101262.8, Granted publication number for CN100370644, Granted publication day are 2008.02.20, the denomination of invention patent for " anode material for lithium-ion batteries and preparation method thereof ", disclose a kind of employing solid phase method and prepared lithium ion battery composite cathode material LiFePO4 LiFePO
4/ C and production method thereof is characterized in that lithium ion battery composite cathode material LiFePO4 LiFePO
4/ C is evenly mixed in proportion by the additive of the conductive additive of lithium source, source of iron, phosphorus source and carbon containing and nanometer, lithium source, source of iron and phosphorus source proportion of raw materials mol ratio are Li: Fe: P=1～1.1: 1～1.02: 1, the consumption percentage by weight 94.9～78% in lithium source, source of iron and phosphorus source, the consumption percentage by weight 5～20% of conductive additive, the consumption percentage by weight 0.1～2% of nanometer additive, the lithium source is a kind of or its mixture of lithium hydroxide, lithium carbonate, lithium oxalate, lithium fluoride, lithium phosphate, lithium acetate, and source of iron is FeC
2O
42H
2O, FeO, Fe
3O
4A kind of or its mixture, the phosphorus source is NH
4H
2PO
4, (NH4)
2HPO
4, P
2O
5A kind of or its mixture, conductive additive is a kind of or its mixture of polypropylene, polyacrylamide, glucose, sucrose, starch, nanometer additive is nanometer SiO
2
Summary of the invention
The purpose of this invention is to provide a kind of anodal aqueous binder that uses and replace conventional P VDF/NMP adhesive, stop pollution to air, environmental protection improves battery cycle life, and can reduce the high lifetime water-soluble lithium rechargeable battery and the manufacture craft thereof of the cost of raw material.
For achieving the above object, the technical solution used in the present invention is:
A kind of high lifetime water-soluble lithium battery comprises: anodal raw material and negative pole raw material is characterized in that: the percentage by weight of described anodal raw material is:
Aqueous binder 2.2%～5.8%;
Electroactive material LiFePO
456%～65%;
Conductive black 2.3%～4.7%;
Deionized water 31%～35.5%;
Viscosity is controlled to be 1800～3200mPas.
According to described high lifetime water-soluble lithium battery, it is characterized in that: the percentage by weight of described anodal raw material is:
Aqueous binder 2.4%～5.1%;
Electroactive material LiFePO
461%～63%;
Conductive black 2.7%～4.2%;
Deionized water 33.1%～34.5%;
Viscosity is controlled to be 2000～3000mPas.
According to described high lifetime water-soluble lithium battery, it is characterized in that: the percentage by weight of described anodal raw material is:
Aqueous binder 2.5%;
Electroactive material LiFePO
460%;
Conductive black 4%;
Deionized water 33.5%;
Viscosity is controlled to be 2100mPas.
According to described high lifetime water-soluble lithium battery, it is characterized in that: the percentage by weight of described anodal raw material is:
Aqueous binder 2.7%;
Electroactive material LiFePO
460%;
Conductive black 3.1%;
Deionized water 34.2%;
Viscosity is controlled to be 2337mPas.
According to described high lifetime water-soluble lithium battery, it is characterized in that: the percentage by weight of described anodal raw material is:
Aqueous binder: 3.0%;
Electroactive material LiFePO
460%;
Conductive black 2.7%;
Deionized water 34.3%;
Viscosity is controlled to be 2433mPas.
According to described high lifetime water-soluble lithium battery, it is characterized in that: described anode pole piece (1) adopts the inner non-equidistant symmetric double aluminium pole ears structure of pole piece, promptly first lug (2) is welded on 1/5 place of anode pole piece (1), and second lug (3) is welded on 3/5 place of anode pole piece (1).
According to described high lifetime water-soluble lithium battery, it is characterized in that: described negative pole raw material comprises MCMB, sodium carboxymethylcellulose, deionized water, conductive black; MCMB, its particle size distribution: D10: 〉=8um, D50:16.5～19um, D90 :≤32um, oxidation processes is carried out on the surface, and promptly the carbon microspheres after 150 ℃ vacuum sintering furnace interior heat is handled 1h carries out surface oxidation treatment 1h in the radio frequency plasma of the oxygen atmosphere of alpha ray-volume degree of depth 20%.
A kind of technology of making described high lifetime water-soluble lithium battery, it is characterized in that: by the percentage by weight of described anodal raw material, with deionized water and aqueous binder stirring at low speed, rotating speed 5～10Hz, 5～10min, high-speed stirred then, rotating speed 30～45Hz, 45～60min adds electroactive material LiFePO
4Vacuumize high-speed stirred with conductive black, vacuum values≤-0.095MPa, rotating speed 30～45Hz, 4～6h obtains the high lifetime water-soluble lithium battery anode sizing agent at last.
High lifetime water-soluble lithium battery positive pole of the present invention replaces traditional N-methyl pyrrolidone adhesive with aqueous binder, employing can be stopped the pollution to air, environmental protection with the anode sizing agent coating of aqueous binder preparation, improve battery cycle life, and can reduce the cost of raw material 20～30%.LiFePO
4Lithium ion secondary battery negative pole selects for use MCMB (CMB-N) to replace traditional negative material, improves lithium ion and take off the embedding performance in negative pole, improves battery cycle life.The anodal inner non-equidistant symmetric double aluminium pole ears structure of pole piece that adopts, it is 1/5,3/5 place that lug is welded on anode pole piece, overcome cylindrical battery because coiling Internal and external cycle tension force unbalanced this difficult problem of current density when differing discharging and recharging of bringing, euqalizing current density when discharging and recharging, effectively reduce internal resistance, improve battery cycle life.Thereby can be brought up to 5000～5500 times in the high lifetime water-soluble lithium battery life-span.Production process of the present invention is easy to control, handling safety, flow process short, raw material are easily purchased, and mature and reliable technically is high in technological content, added value is big.
Description of drawings
Fig. 1 is a process chart of the present invention.
Fig. 2 is the structural representation of anode pole piece of the present invention.
In the accompanying drawing: 1, anode pole piece; 2, first lug; 3, second lug.
Embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments:
The anodal raw material of the present invention uses aqueous binder to replace conventional P VDF/NMP adhesive, adopts non-equidistant symmetric double aluminium pole ears structure; Simultaneously to making technology negative material-MCMB (particle size distribution: D10: 〉=8um of high lifetime water-soluble lithium battery most critical, D50:16.5～19um, D90 :≤32um), (carbon microspheres after 150 ℃ vacuum sintering furnace interior heats are handled 1h is at the oxygen (α-20vol%O of alpha ray-volume degree of depth 20% to carry out surface oxidation treatment
2) carry out surface oxidation treatment 1h in the radio frequency plasma of atmosphere).
High life lithium ion secondary battery positive electrode of the present invention uses the slurry coating of aqueous binder preparation, positive pole replaces traditional N-methyl pyrrolidone adhesive (PVDF/NMP) with aqueous binder, can stop pollution to air, environmental protection, improve battery cycle life, and can reduce the cost of raw material 20～30%.
The commercially available prod that aqueous binder among the present invention can select for use Beijing skill Development Co., Ltd of Pai En Cisco to produce, aqueous binder are generally made by F105-modification Arabic gum and F105A-improvement property silica gel.Wherein: F105-modification Arabic gum plays suspension, anti-precipitation; F105A-improvement property silica gel plays bonding effect.The quality proportioning of F105-modification Arabic gum and F105A-improvement property silica gel is generally 4～5 in the aqueous binder: 1, and the present invention can select for use 5: 1.
Anode pole piece of the present invention adopts the inner non-equidistant symmetric double aluminium pole ears structure of pole piece, and as shown in Figure 2, promptly first lug 2 is welded on 1/5 place of anode pole piece 1, and second lug is welded on 3/5 place of anode pole piece 1.Anode pole piece adopts the inner non-equidistant symmetric double aluminium pole ears structure of pole piece, overcomes cylindrical battery because coiling Internal and external cycle tension force unbalanced this difficult problem of current density when differing discharging and recharging of bringing effectively reduces internal resistance, improves battery cycle life.Thereby can be brought up to 5000～5500 times in the high lifetime water-soluble lithium battery life-span.
High life ion secondary battery cathode material lithium of the present invention selects for use MCMB (CMB-N) to replace traditional negative material, improves lithium ion and take off the embedding performance in negative pole, improves battery cycle life.MCMB (CMB-N), particle size distribution: D10: 〉=8um, D50:16.5～19um, D90 :≤32um.The present invention carries out surface oxidation treatment to MCMB (CMB-N), that is: the carbon microspheres after 150 ℃ vacuum sintering furnace interior heat is handled 1h is at the oxygen (α-20vol%O of alpha ray-volume degree of depth 20%
2) carry out surface oxidation treatment 1h in the radio frequency plasma of atmosphere.
Technological process of the present invention as shown in Figure 1, with aqueous binder and deionized water mixed liquor, electroactive material LiFePO
4, conductive black drops in the charging basket, to be mixedly is coated with, dries after evenly, obtains anode pole piece; In like manner, sodium carboxymethylcellulose (CMC) and deionized water mixed liquor, MCMB (CMB-N), conductive black are dropped in the charging basket, mix, coating, oven dry obtain cathode pole piece.Then, respectively with its roll-in, divide and to be cut to small pieces, behind the lug of burn-oning anode pole piece wrapped in the cathode pole piece and reels, goes into shell, slot rolling and fluid injection, seal, make its outward appearance one-step forming just, again battery pre-charging is carried out partial volume by its amount of capacity, carry out the detection of product at last.
1, anodal raw material:
In the anodal crude material technology formula (percentage by weight):
Aqueous binder 2.2%～5.8%;
Electroactive material LiFePO
456%～65%;
Conductive black 2.3%～4.7%;
Deionized water 31%～35.5%;
Viscosity is controlled at 1800～3200mPas.
Aqueous binder mass ratio: F105: F105A=4～5: 1.
2, manufacture craft: deionized water and aqueous binder stirring at low speed (rotating speed 5～10Hz, 5～10min), then high-speed stirred (rotating speed 30～45Hz, 45～60min), add electroactive material LiFePO
4With conductive black vacuumize high-speed stirred (vacuum values≤-0.095MPa, rotating speed 30～45Hz, 4～6h) obtain the high lifetime water-soluble lithium battery anode sizing agent at last.
3, through in repeatedly testing, finding the appropriate process prescription: aqueous binder 2.4%～5.1%; Electroactive material LiFePO
461%～63%; Conductive black 2.7%～4.2%; Deionized water 33.1%～34.5%; Viscosity is controlled at 2000～3000mPas.
Optimum process condition is: vacuumize, the reaction time is 4.5～5h, and resulting slurry is best.
Embodiment 1:
1. raw material:
Anodal raw material: aqueous binder, deionized water, electroactive material, conductive black, aluminium foil.
Negative pole raw material: MCMB (CMB-N), sodium carboxymethylcellulose (CMC), deionized water, conductive black, Copper Foil.
2. fill a prescription:
Aqueous binder: 2.5%; Electroactive material LiFePO
460%; Conductive black 4%; Deionized water 33.5%; Viscosity is controlled at 2100mPas.
3. production method: by anode formula aqueous binder is dropped in the charging basket, open agitating device, add deionized water and conductive black and vacuumize stirring, add electroactive material LiFePO then
4Vacuumize to stir and obtain anode sizing agent; In like manner, prepare cathode size according to this.Then slurry is coated with (anode sizing agent is applied to aluminium foil, negative pole is applied on the Copper Foil), oven dry, with roll-in, divide the pole piece the cut lug of burn-oning to reel, go into shell, fluid injection, seal, make its outward appearance one-step forming just, again battery pre-charging is carried out partial volume by its amount of capacity, carry out the detection of product at last.
Embodiment 2:
Raw material is identical with embodiment 1
Prescription:
Aqueous binder: 2.7%; Electroactive material LiFePO
460%; Conductive black 3.1%; Deionized water 34.2%; Viscosity is controlled at 2337mPas.
Production method: with embodiment 1
Embodiment 3 (most preferred embodiment):
Raw material is identical with embodiment 1
Prescription:
Aqueous binder: 3.0%; Electroactive material LiFePO
460%; Conductive black 2.7%; Deionized water 34.3%; Viscosity is controlled at 2433mPas
Production method: with embodiment 1
Through experimental results demonstrate that embodiment 3 is preferred plan.
Embodiment recited above is described preferred implementation of the present invention; be not that design of the present invention and protection range are limited; under the prerequisite that does not break away from design concept of the present invention; common engineers and technicians make technical scheme of the present invention in this area various modification and improvement all should fall into protection scope of the present invention.
Claims (8)
1, a kind of high lifetime water-soluble lithium battery comprises: anodal raw material and negative pole raw material is characterized in that: the percentage by weight of described anodal raw material is:
Aqueous binder 2.2%～5.8%;
Electroactive material LiFePO
456%～65%;
Conductive black 2.3%～4.7%;
Deionized water 31%～35.5%;
Viscosity is controlled to be 1800～3200mPas.
2, high lifetime water-soluble lithium battery according to claim 1 is characterized in that: the percentage by weight of described anodal raw material is:
Aqueous binder 2.4%～5.1%;
Electroactive material LiFePO
461%～63%;
Conductive black 2.7%～4.2%;
Deionized water 33.1%～34.5%;
Viscosity is controlled to be 2000～3000mPas.
3, high lifetime water-soluble lithium battery according to claim 1 is characterized in that: the percentage by weight of described anodal raw material is:
Aqueous binder 2.5%;
Electroactive material LiFePO
460%;
Conductive black 4%;
Deionized water 33.5%;
Viscosity is controlled to be 2100mPas.
4, high lifetime water-soluble lithium battery according to claim 1 is characterized in that: the percentage by weight of described anodal raw material is:
Aqueous binder 2.7%;
Electroactive material LiFePO
460%;
Conductive black 3.1%;
Deionized water 34.2%;
Viscosity is controlled to be 2337mPas.
5, high lifetime water-soluble lithium battery according to claim 1 is characterized in that: the percentage by weight of described anodal raw material is:
Aqueous binder: 3.0%;
Electroactive material LiFePO
460%;
Conductive black 2.7%;
Deionized water 34.3%;
Viscosity is controlled to be 2433mPas.
6, high lifetime water-soluble lithium battery according to claim 1, it is characterized in that: described anode pole piece (1) adopts the inner non-equidistant symmetric double aluminium pole ears structure of pole piece, promptly first lug (2) is welded on 1/5 place of anode pole piece (1), and second lug (3) is welded on 3/5 place of anode pole piece (1).
7, according to claim 1,2,3,4 or 5 described high lifetime water-soluble lithium batteries, it is characterized in that: described negative pole raw material comprises MCMB, sodium carboxymethylcellulose, deionized water, conductive black; MCMB, its particle size distribution: D10: 〉=8um, D50:16.5～19um, D90 :≤32um, oxidation processes is carried out on the surface, and promptly the carbon microspheres after 150 ℃ vacuum sintering furnace interior heat is handled 1h carries out surface oxidation treatment 1h in the radio frequency plasma of the oxygen atmosphere of alpha ray-volume degree of depth 20%.
8, a kind of technology of making claim 1,2,3 or 4 described high lifetime water-soluble lithium batteries, it is characterized in that: by the percentage by weight of described anodal raw material, with deionized water and aqueous binder stirring at low speed, rotating speed 5～10Hz, 5～10min, high-speed stirred then, rotating speed 30～45Hz, 45～60min adds electroactive material LiFePO
4Vacuumize high-speed stirred with conductive black, vacuum values≤-0.095MPa, rotating speed 30～45Hz, 4～6h obtains the high lifetime water-soluble lithium battery anode sizing agent at last.
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| CN102145329A (en) * | 2011-03-14 | 2011-08-10 | 中航锂电（洛阳）有限公司 | Slurry mixing process of lithium ion battery electrode slurry |
| CN102306782A (en) * | 2011-08-08 | 2012-01-04 | 深圳市沃特玛电池有限公司 | Lithium iron phosphate battery anode and preparation method thereof |
| CN102637840A (en) * | 2012-04-12 | 2012-08-15 | 北京神州远望科技有限公司 | Intelligent diving lithium battery pack with pressure compensating device and preparation method thereof |
| CN102862973A (en) * | 2012-08-16 | 2013-01-09 | 广东东岛新能源股份有限公司 | Method for preparing negative electrode material of lithium ion battery from mesophase carbon micro beads |
| CN103208630A (en) * | 2012-01-11 | 2013-07-17 | 襄阳正信航空技术有限公司 | Hydrosolvent type lithium iron phosphate battery anode material |
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