CN106450169A - Manufacturing method of negative plate of safety lithium-ion battery - Google Patents

Manufacturing method of negative plate of safety lithium-ion battery Download PDF

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Publication number
CN106450169A
CN106450169A CN201610782741.9A CN201610782741A CN106450169A CN 106450169 A CN106450169 A CN 106450169A CN 201610782741 A CN201610782741 A CN 201610782741A CN 106450169 A CN106450169 A CN 106450169A
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China
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lithium ion
ion battery
battery
mixture
negative electrode
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林定文
张文博
舒方君
丁先红
周环波
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Hubei Uee Energy Technology Co Ltd
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Hubei Uee Energy Technology Co 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
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a manufacturing method of a negative plate of a safety lithium-ion battery. The method comprises the steps of mixing a negative active material with a conductive agent at a certain mass ratio to obtain a mixture A; carrying out ball-milling and mixing on an additive B and the mixture A at a certain mass ratio to form a mixture C; preparing a certain mass percent of water solution from CMC which accounts for a certain mass ratio of the mixture C, carrying out constant-temperature stirring, adding an SBR which accounts for a certain mass ratio of the mixture C in batches, simultaneously adding an NMP which accounts for a certain ratio of the mixture C and carrying out constant-temperature stirring to form a sizing material D; adding the mixture C to the sizing material D in batches, controlling the solid content of the mixture C and stirring to obtain slurry; adding a proper amount of water, adjusting, controlling the viscosity and stirring to obtain negative slurry E; employing copper foil as a current collector F, intermittently coating a single side or double sides of the current collector F with the negative slurry E, reserving a certain current collector, carrying out drying, controlling the surface density, carrying out rolling and controlling the compactness and the thickness of the negative plate; and dividing, cutting, welding and pasting a tab adhesive tape to obtain the negative plate of the safety lithium-ion battery. The lithium-ion battery assembled by the negative plate has good electric cycle performance and safety performance.

Description

A kind of manufacture method of safety lithium ion cell negative plate
Technical field
The present invention relates to cell art, it is more particularly to a kind of manufacture method of safety lithium ion cell negative plate.
Background technology
Lithium ion battery mainly (includes stainless steel case, plastic housing by positive and negative electrode pole piece, barrier film, electrolyte and battery container And aluminum plastic film flexible package etc.) part composition.Wherein, manufacture lithium ion battery negative electrode negative electrode active material be mainly " my god So negative pole graphite " or " modified graphite " or " Delanium ", and CNT, Graphene etc., the synthetic technology of graphite material, The processing of material and chemical property etc., relative contrast is more stable, ripe.The source of native graphite is also compared with horn of plenty thus price One of cheap, but be also the critical material of lithium ion battery, it is that the impact of the combination property to lithium ion battery has a major impact One of material, major influence factors are both positive and negative polarity technical recipe and technical management etc..Additionally, lithium ion battery separator, electrolysis Liquid be also impact battery performance critical material, barrier film mostly be macromolecular material (predominantly polythene PE, polypropylene PP or PP/PE/PP composite membrane, and Al2O3Ceramic modified polymer separators etc.), diaphragm material correlation technique also comparative maturity；Electrolysis Liquid technology also comparative maturity, disclosure satisfy that the fundamental need of the production of lithium ion battery and application at this stage.But, positive-active Material, barrier film, the physicochemical property of three kinds of core materials of electrolyte, determine existing associated materials and all can not definitely ensure lithium ion The security performance of battery.The application both positive and negative polarity pole material that more heat stability is higher, chemical property is more stable, technical recipe are solutions Certainly one of lithium ion battery safety performance most efficient method.
Compare with traditional one-shot battery and secondary accumulator battery, because relatively advanced lithium ion battery has single battery core battery Voltage is high, specific capacity is high, specific energy is high, specific power is high, charge-discharge performance is good, storge quality is excellent, specific energy and compare energy Numerous distinguishing feature such as metric density height, and it is widely used in electric tool, movable electrical appliances, model plane, unmanned plane, electric automobile The field such as electrical source of power and portable power source, emergency standby power.Set with lithium ion battery related application technical field electrical equipment The development further of standby and device, thin, light, high-energy, high power density, high circulation performance requiring lithium ion battery to have On the basis of, high high security to battery is it is proposed that higher requirement；It is electric automobile field by it, to lithium ion battery Security performance is put forward higher requirement.Negative electrode active material note used by business-like lithium ion secondary battery positive electrode at this stage Meaning is the materials such as graphite, modified graphite and Graphene, CNT.
Essentially from two aspects, one is the potential safety hazard that battery performance itself determines to the potential safety hazard of lithium ion battery. The positive active material of currently manufactured used in battery is oxidizing substance (the particularly LiCoO that can slowly decomposite oxygen2 Deng)；Electrolyte solvent is inflammable reductive organic matter (carbonats compound), electrolyte (predominantly LiPF6) for meeting water Facile hydrolysiss generate extremely corrosive, oxidisability HF；Barrier film is also that heat is easily shunk, easily melts, inflammable macromolecular material (is led Polyethylene to be, polypropylene etc.).These are that commercial Li-ion batteries exist at this stage, intrinsic internal urgently to be resolved hurrily is asked Topic.It two is that the misuse of lithium ion battery, abuse (overcharge, cross and put, short circuit, high temperature, burning, vibrations, extrude, fall, clashing into Deng) or product quality problem (residual air, residual water, internal short-circuit, poorly sealed real, shell is damaged, not prison welding etc. Deng) potential safety hazard that leads to.
In order to eliminate the above-mentioned potential safety hazard existing for lithium ion battery, produce function admirable, high security lithium from Sub- battery, those skilled in the relevant art mainly from research and development are stable, safer lithium ion battery plus-negative plate material, fire-retardant electrolysis The aspect effort such as liquid, stable electrolyte, fire-retardant barrier film, exploitation new type lithium ion battery system.Additionally, person skilled also from The construction of lithium ion battery is started with and is improved, to improve the security performance of lithium ion battery.
Document " lithium ion battery safe practice summarizes [J] " (electronic product reliability and environmental test, 2012,30 (2): 48-51) describe safety reasons analysis, lithium ion battery safe practice of lithium ion battery product etc.；The document mainly from " from the higher raw material of safety coefficient：The selection of positive electrode, diaphragm material, electrolyte " etc. and " battery core general safety sets Meter：Both positive and negative polarity Capacity Ratio and designed size piece, barrier film width have surplus, insulation processing and relief valve setting " etc. aspect carry out Summary.Document " lithium ion battery safety problem is expected to solve [J] " (power technology, 2011,135 (7)：759-761) describe The content of three aspects such as lithium ion battery security status, the Japan-US solution taken and concrete solution；It proposes Concrete solution include：Using qualified positive and negative pole material, improve the stability of electrode material；It is electrolysed using flame retardant type Liquid；The battery diaphragm more excellent from mechanically and thermally closing performance；Change design and improve battery heat-sinking capability；Strict production process And the strict use of battery etc..The document does not provide practicable technological parameter and the work of secure lithium ion battery Skill condition etc..Document " lithium ion battery safety [J] " (power technology, 2009,133 (1)：7-9) also review " impact lithium ion Three aspects such as the factor of battery security, the impact of different positive electrode and the measure improving lithium ion battery security " Problem.The document is equally not directed to the practicable concrete technology improving lithium ion battery security and enforcement technical parameter Deng.Document " lithium ion battery safety performance studies [J] " (chemical progress, 2011,23 (2/3)：401-409) have studied " electrode The heat stability of material：Reaction between negative pole and electrolyte；Reaction between positive pole and electrolyte, the heat stability of electrolyte With combustibility；Failure effect factorial analysiss abused by battery：Overcharge, hot tank (simulate improper applied at elevated temperature), acupuncture, extruding short with interior The contents such as road ".The document is reached a conclusion：Reaction between negative pole and electrolyte includes：SEI film (Solid Electrolyte Interface, solid electrolyte interface film) decomposition, the reaction of the lithium of embedded negative pole and electrolyte, the lithium of embedded negative pole with glue Connect the reaction of agent；Select heat stability higher (as LiFePO4Deng) positive electrode improve lithium ion battery safety；Using The higher lithium salts of heat stability adds flame-retardant additive etc. as in the electrolyte of lithium ion battery and electrolyte；Lithium is on electrode Segregation be cause inside lithium ion cell short circuit main cause.Document " safety problem [J] of part lithium ion battery " (electricity Pond, 2008,38 (1)：25-26) have detected the safety of part commercial Li-ion batteries.The document is mainly existed by simulated battery Actual shipment condition in transportation, to lithium ion battery it may happen that the probability of blast is studied.The inspection of this article Survey result to show：On market, part lithium ion battery still suffers from certain potential safety hazard.Document " lithium ion battery overcharge safety Resist technology studies [A] " (energy storage of Second Committee China and electrokinetic cell and its critical material science and technology investigation and exchange of technology Meeting, Chinese Chengdu, 2007：92) brief " oxidation polymerization short circuit (breaking), oxidation-reduction pair shuttling agent, temperature sensitivity The concepts such as electrode, potential-sensitive separator ".
Document " High-safety lithium-sulfur battery with prelithiated Si/C anode And ionic liquid electrolyte [J] " (Electrochimica Acta, 2013,91:58-61) describe one kind Lithium-sulfur system the lithium ion battery of the ion electrolyte with Si/C as negative pole of high security.Document " A Novel Cathode Material with a Concentration-Gradient for High-Energy and Safe Lithium-Ion Batteries [J] " (Adv.Fun.Mater., 2010,20:485-491) report mutual doping between a kind of new nickel cobalt manganese Binary and tertiary cathode material, predominantly：Safer high-performance lithium ion battery can be manufactured.Document " Inorganic thin layer coated porous separator with high thermal stability for safety Reinforced Li-ion battery [J] " (Journal of Power Sources, 2012,212：22-27) describe The research of the performance of the lithium ion battery separator of coating inorganic coating in organic barrier film, to improve the safety of lithium ion battery Energy.Document " Ultrathin Coatings on Nano-LiCoO2for Li-Ion Vehicular Applications [J] " (Nano Lett., 2011,11：414-418) report：In nanometer LiCoO2Material surface coats ultra-thin Al2O3Inorganic matters To improve LiCoO2The research of the discharge and recharge security performance of the high-rate charge-discharge capability of material and battery.Document " A Novel Cathode Material with a Concentration-Gradient for High-Energy and Safe Lithium-Ion Batteries [J] " (Adv.Funct.Mater., 2010,20：485 491) report one kind and there is high energy Metric density, Ni, Co, Mn ternary spherical anode material of the anode material for lithium-ion batteries high concentration gradient of high security, positive pole The elements such as Mn, Ni, Co of material granule are from content core to shell incremented by successively (referring to its Fig. 4)；This material can improve Mn positive pole material The stable circulation performance of material and the security performance of battery.Document " A safe, high-rate and high-energy polymer lithium-ion battery based on gelled membranes prepared by electrospinning[J]”(Energy Environ.Sci.,2011,4：921 927) report one kind polyvinyladine floride Electrostatic weave barrier film, nanoscale Sn-C base negative pole and the technology of battery manufactured by spinel-type nickel lithium manganate cathode material and The research of correlated performance；The document claims：With the lithium ion battery manufactured by the technology of document report, not only there is high-energy close The excellent performance capability such as aspects such as degree, high power, and there is high circulation life-span and high security.Document " Challenges in the development of advanced Li-ion batteries:a review[J]”(Energy Environ.Sci., 2011,4：3243 3262) review the significant challenge facing of lithium ion battery development.The document is recognized For：The security performance improving lithium ion battery is field of lithium ion battery most significant problems urgently to be resolved hurrily.Document " Safe and fast-charging Li-ion battery with long shelf life for power applications[J]” (J.Power Sources,2011,196:3949 3954) report with LiFePO4For positive active material with Li4Ti5O12 For negative electrode active material the security performance of lithium ion battery and the high-rate charge-discharge capability of battery.The document claims：Such Type lithium ion battery has preferable high-rate charge-discharge capability, higher capability retention and preferable security performance.Document “Ultrathin Direct Atomic Layer Deposition on Composite Electrodes for Highly Durable and Safe Li-Ion Batteries [J] " (Adv.Mater.2010,22,2172 2176) have studied one kind Tool high circulation life-span and the anode material for lithium-ion batteries of high safety performance, that is, in LiCoO2Surface depositing Al2O3The material of atomic layer Material；Report Al2O3Layer is conducive to improving the charge-discharge performance of lithium cobaltate cathode material and the safety of battery.Document “Hollow Nanostructured Anode Materials for Li-Ion Batteries[J]”(Nanoscale Res.Lett.2010,5:1525 1534) review hollow nanostructures negative material to raising lithium ion battery safety performance Correlational study.Show：Hollow electrode material has that lithium ion diffusion path is short, charge-discharge performance is more excellent, but hollow material tool There are side reaction, heat stability difference and the relatively low defect of volume energy density.Document " Solution-Combustion Synthesized Nanocrystalline Li4Ti5O12As High-Rate Performance Li-Ion Battery Anode[J]”(Chem.Mater.2010,22(9):2857 2863) describe synthesis nanometer Li4Ti5O12 lithium ion battery to bear The correlational study of pole material, has certain application value to the chemical property and security performance improving lithium ion battery.Document “High voltage spinel oxides for Li-ion batteries:From the material researchto the application[J]”(J.Power Sources,2009,189:344 352) report research LiNi0.5Mn1.5O4's Synthetic material, structure and performance；Think：LiNi0.5Mn1.5O4The security performance of material and cost are better than cobalt acid lithium LiCoO2Material Material.Document " Electrochemical Kinetics and Safety of 2-Volt Class Li-Ion Battery System Using Lithium Titanium Oxide Anode[J]”(J.Electrochem.Soc.,2009,156(2): A128-A132) report：Li-Ti oxide Li as lithium ion battery negative material4/3Ti5/3O4(LTO) compared with graphite cathode Material, has good charge-discharge performance and security performance.Document " Performance of Bellcore ' s plastic Rechargeable Li-ion batteries [J] " (Solid State tonics, 1996,86-88：49-54) report A kind of fluorinated polymer liquid electrolyte solution base lithium ion battery.This lithium ion battery weight or volume energy density is high, follows Ring life-span length, power rate and self-discharge rate are excellent, and the manufacture shape of battery is bigger, motility and have extensibility, and has Compared with high safety characteristic.Document " A review on the separators of liquid electrolyte Li-ion batteries[J]”(J.Power Sources,2007,164:351 364) review liquid electrolyte lithium ion battery barrier film Research situation.The document thinks：Although lithium ion battery separator is not involved in electrode electro Chemical reaction, the performance of barrier film Directly affect the chemical property of battery and the safety of battery.Document is further contemplated that：PE (polyethylene), PP (polypropylene) etc. Macromolecular material barrier film fusing point is low, and (general fusing point respectively may be about：90～130 DEG C and 165 DEG C) it is impossible to ensure lithium ion battery Work safety；Ceramic barrier film be have most researching value, ensure lithium ion battery safety performance one, the most promising every One of film.Document " Safe Li-ion polymer batteries for HEV applications [J] " (J.Power Sources,2004,134:124 129) report one kind with the natural stone of double (fluorine sulphonyl) imine lithium electrolytic liquid electrolyte Ink/PEO base gel electrolyte/ferric phosphate lithium cell.Claim according to the document：This kind of ion battery has good electrochemistry cyclicity Energy and higher safety.Document " Dichalcogenide Nanotube Electrodes for Li-ion Batteries [J] " (Adv.Mater., 2002,14 (21)：1531 1534) report a kind of MoS2-xSulfide nano-tube electrode material.According to Report, this material can preferably embed or deviate from lithium ion, and the lithium ion battery of manufacture also has higher security performance.
Lot of domestic and international patent of invention also discloses that the key technology of the security performance about lithium ion battery.Wherein, in State's patent " a kind of manufacture method [p] of safe lithium ion power battery anode pole piece " (number of patent application 201511020032.9) Disclose a kind of manufacture method of safe lithium ion power battery anode pole piece.The disclosure technology is main multiple new by applying Type positive electrode and the new design of anode pole piece, to reach the purpose improving lithium ion battery safety performance.Chinese patent is " a kind of The manufacture method [p] of safe lithium ion electrokinetic cell " (number of patent application 201511020031.4) the disclosure technology is mainly logical Cross the new design of both positive and negative polarity pole piece structure, the modified and safe electrolyte of positive and negative pole material, application of blowout disk etc., reach The requirement of safety lithium ion cell." a kind of positive pole adds the safety lithium-ion electric of nanotrees lipid oxidizing solids to Chinese patent Pond and preparation method thereof [p] " (number of patent application 201510262521.9) discloses a kind of safety lithium ion cell and its preparation Method.The disclosure technology mainly uses adds based resin, epoxy resin, phenolic resin and APP in positive electrode Or the fire retardant such as tetrabromobisphenol, reach the raising stability of positive electrode and the purpose of lithium ion battery security.Chinese patent " safety lithium ion cell [P] " (number of patent application 201510269595.5) discloses a kind of cylinder " safety lithium ion cell " Manufacturing technology.Technology concrete measure disclosed in this patent is：Design so-called safeguard construction, that is, include a safe floor, Multiple spicules, spicule are arranged in so-called elastic layer has multiple most advanced and sophisticated, multiple most advanced and sophisticated sensing battery cores.This design is Whole technical purpose is that battery battery core expands in extreme circumstances, and the most advanced and sophisticated battery core that pierces through causes internal short-circuit, thus " ensureing to realize The safety of lithium ion battery ".Chinese patent " the good safety lithium ion cell of a kind of cyclicity [P] " (number of patent application 201310574669.7).Disclosed in this patent, technology concrete scheme is：Positive/negative plate surface is each coated with polymer support and applies Layer, negative pole adopts carbon, stannum nano-fiber composite film material.It is said that：The disclosure technology can greatly suppress electrode material efflorescence, Burst apart and reunite, so as to improve the cycle performance of electrode material and the stability ensureing electrode, obtain reversible specific capacity and follow Ring performance good negative material, intercepts because polymer support coating produces, it is to avoid the short circuits that both positive and negative polarity contact two causes are (in detail See its summary part).Chinese patent " a kind of highly secure lithium ion battery and preparation method thereof [P] " (number of patent application 201310587842.7) disclosing a kind of highly secure lithium ion battery and preparation method thereof, its step includes：Make flexible-packaged lithium Ion battery single battery core, the single or multiple flexible packing lithium ion battery battery core made is loaded in battery case, close Envelope, extracts air in battery out, is filled with noble gases, and holding inside battery is malleation, sealing.It is said that：This technology can be from The burning fundamentally prevent, avoiding outside batteries oxygen to enter and the causing even potential safety hazard such as blast.Chinese patent is " a kind of high Capacity, high magnification, the manufacture method [P] of highly secure lithium ion battery " (number of patent application 201310107873.8) discloses one Plant the manufacturing technology of lithium ion battery.Its technological core is：Add silicon dioxide, aluminium sesquioxide in collector.To improve The security performance of the lithium ion battery manufacturing.Chinese invention patent " the aluminum method for coating of highly secure lithium ion battery positive electrode [P] " (number of patent application 201110314350.1) discloses a kind of method of the anode material for lithium-ion batteries manufacturing cladding aluminum. It is said that：This technology can make anode material for lithium-ion batteries ensure its high temperature storage safety under high charge blanking voltage, follow Ring stability (refers to its summary).A kind of Chinese patent " safety lithium ion cell [P] " (number of patent application 201110260367.3) disclose a kind of safety lithium ion cell.Particular technique measure disclosed in this patented technology is：In electricity Add " polyethylene and conductive agent " combined conductive agent of constituting so that lithium ion battery is in overcharge, overdischarge, disconnected in the material of pole In road extruding, acupuncture or falling process overheated when, the polyethylene of combined conductive agent melts, so that conductive agent loses leading Electrical property, stops the overheated issuable potential safety hazard of lithium ion battery, reaches the purpose improving battery security.Chinese patent " a kind of safety lithium ion cell [P] " (number of patent application 201110258312.9) discloses a kind of safety lithium ion cell.Should Technical measures disclosed in patent are：Add polypropylene, polyethylene etc. and make so-called compound-type conducting high score in conductive agent Sub- material, conducting polymer collision in extraordinary circumstances, thus destroying conductive network, stops lithium ion battery from crossing the electricity of thermal initiation The generation of pond security situation.Chinese patent " safety lithium ion cell [P] " (number of patent application 201110260368.8) discloses A kind of " safety lithium ion cell ".Its concrete grammar is：In electrode active material add combined conductive agent, combined conductive agent by Polyethylene Particles matrix material and the granule of plated metal skin-material composition；Claim according to this patent of invention technology：This invention is not only Can overcharging, cross put, short circuit, extruding, acupuncture or when falling and leading to lithium ion battery overheated, cell resistance increases and improves safety Property, and in battery thermal runaway, combined conductive agent melts and loses electric conductivity, and cut-out circuit is it is ensured that battery security (refers to Its summary).
United States Patent (USP) " Method and system for determining and charging Li-ion Battery in an integrated power system [P] " (number of patent application 8,330,413,2012.12.11) is open A kind of " determination of lithium ion battery and charging method and system in integrated power system ", i.e. lithium-ion battery system management system System, to improve work efficiency and the safety of lithium ion battery.United States Patent (USP) " Ferrous phosphate powders, lithium iron phosphate powders for li-ion battery,and methods for Manufacturing the same [P] " (number of patent application 9,059,464,2015.6.16) open one kind " lithium ion battery Positive electrode and lithium ion battery manufacture method and correlation technique ".The disclosure technology is mainly by preparing iron phosphate and iron phosphate Lithium powder manufactures lithium ion battery (referring to its description " BACKGROUND " part), to improve the performance of lithium ion battery.Beautiful State's patent " Li-ion battery and battery active components on metal wire [P] " (patent Shen Please numbers 8,993,172,2015.3.31) disclose a kind of " lithium ion battery and attachment cell active materials on the metal filament ". Its particular technique measure is the electrode active material such as depositing silicon silicon on a diameter of 5～500 μm of tinsel, manufactures lithium with this Ion battery electrode and lithium ion battery, (refer to its description with the chemical property and safety improving lithium ion battery " SUMMARY OF THE INVENTION " part and Figure of description 1～11).United States Patent (USP) " Material Engineering for high performance Li-ion battery electrodes [P] " (number of patent application 8, 906,576,2014.9.9) disclose the technology of a kind of " high performance lithium ion battery electrode material ".The disclosure technology concrete Measure is：Prepare stable porous Carbon anode (referring to its description " Abstract " part to describe) with plasma technique.With Improve charge-discharge performance and the safety of battery.
United States Patent (USP) " Ferrous phosphate (II) powders, lithium iron phosphate powders For Li-ion battery, and methods for manufacturing the same [P] " (number of patent application 8, 481,211,2013.7.9) disclosed in, technology thinks：To manufacture the higher ferrous phosphate of stability, lithium iron phosphate positive material, The security performance that lithium ion battery can be effectively improved (refers to：Description Description of Related Art part).Beautiful State's patent " Li-ion battery with anode current collector coating [P] " (number of patent application 8, 563,173,2013.10.22) disclosed in, technology thinks：Lithium ion battery internal resistance height, short circuit, membrane ruptures, negative pole dendrite, ring Border high temperature etc. is all that the key factor causing cell safety hidden danger (refers to its description " BACKGROUND " part the 4th～the 6th Natural segment description).The concrete technical scheme of the disclosure technology is：Coating simple metal or alloy, conduction on negative current collector Metal-oxide or such as Indium sesquioxide., zinc oxide and sulfide etc., this coating can effectively suppress the production of Li dendrite, thus carrying (description and the description that refer to its description " DESCRIPTION " part are attached for the cycle life of high-lithium ion battery and safety Figure).United States Patent (USP) " Gel polymer Li-ion battery electrode slice and preparation method Thereof [P] " (number of patent application 8,343,655,2013.1.1) settles sth. according to policy or law a kind of " electrode plate of gel polymer lithium ion battery And preparation method thereof ".The disclosure technology concrete measure is：Lithium ion battery plus-negative plate pole is prepared using multilamellar one step coating technique Piece, strengthens homogeneity and the stability of pole piece, improves battery with two side terminals, thus the safety improving lithium ion battery (refers to Its description " SUMMARY OF THE INVENTION " partly paragragh second from the bottom).United States Patent (USP) " Li-ion battery With porous anode support [P] " (number of patent application 8,426,052,2013.4.23) discloses one kind and " has many The lithium ion of hole negative pole " technology.The disclosure technology thinks：The fracture of anode electrode slice is lithium ion battery potential safety hazard factor One of (referring to description " BACKGROUND " partly paragragh second from the bottom).The particular technique measure of therefore this patent of invention It is：Electrode fabrication adopts rigid current collector, in other words collector be rigid support frame (the rigid support frame, Refer to its " Abstract " part and Figure of abstract), to improve the stability of battery electrode, and then improve the peace of lithium ion battery Quan Xing.United States Patent (USP) " In cycling stability of Li-ion battery with molten salt The open molten salt electrolyte of electrolyte [P] " (number of patent application 7,267,908,2007.9.1) replaces conventional organic solution The technology of liquid.The disclosure technology thinks：Molten salt electrolyte generally has high-melting-point and low steam pressure, and therefore they have The higher safety than organic electrolyte, the lithium ion battery of manufacture also has accordingly higher safety.
The comprehensive existing both at home and abroad feature about lithium ion battery safe practice is it is therefore apparent that prior art presence is as follows Clearly disadvantageous or defect：
1st, the existing technology improving lithium ion battery security, is much all utilized in positive and negative pole material increasing conductive agent Blocking-up additive, that is, utilize macromolecule organic high temperature melt thus blocking electrode electron transmission macromolecular material add Agent etc..This kind of technology there will naturally be clearly disadvantageous and defect：The internal resistance that increased electrode, the volume ratio specific volume reducing battery Amount or specific energy, increased manufacturing technology cost, impact circulating battery service life etc..
2nd, the change of lithium ion battery various types of respective material performance, not only increases the manufacturing technology cost of material With raw material manufacturing cost, and increased the complexity of battery manufacturing process and manufacturing cost it is impossible to from being to solve lithium at all The potential safety hazard of ion battery.
3rd, material improvement technology such as electrolyte, barrier film etc., in the case of increasing technology and the cost of raw material, not only increases The internal resistance of battery, changes the inherent advantage of lithium ion battery, also cannot fundamentally or comprehensively eliminate battery flatulence, short Road, extreme case misuse, extreme accident and extreme environment lithium ion battery it may happen that security incident.
4th, battery management system is not originally field of batteries or the soluble problem of battery person skilled, because electric Pond management system is related to the correlative technology fields such as the management of physics low pressure, computer software design, and battery process technical staff is powerless Solve Related Technical Issues, therefore, be not related to battery process category.Obviously, battery management system can not solve lithium ion at all The safety problem that battery exists.
5th, the lithium ion battery heavy-current discharge effect that prior art manufactures is poor, capacity is low, cycle performance is poor it is impossible to meet Pure electric automobile, hybrid vehicle, electric bicycle etc. are good to lithium ion battery fast charging and discharging, heavy-current discharge effect Require.Additionally, prior art processes flow process is complex, long the production cycle and manufacturing cost higher it is impossible to meet 21 century collection The requirement that reduction produces.
Content of the invention
In order to solve the above-mentioned safety problem that existing field of lithium ion battery exists, the technology of the present invention is not expanding lithium ion Battery manufacturing process technology category, do not change lithium ion battery manufacture conventional process flow on the premise of, the purpose of the present invention It is to there are provided a kind of manufacture method of safe lithium ion power battery cathode piece, the new stone of present invention application lithium ion battery Ink/activated carbon composite anode active material, Technology is simple, and electrode structure is simple, and the manufacturing cycle is short, and energy consumption is low, significantly Improve lithium ion battery charging and discharging capacity, charge and discharge circulation life, the particularly high current of power lithium-ion battery, high power Rate discharge performance, and the job security of lithium ion battery can be significantly increased, significantly reduce lithium-ion-power cell Security risk.It is easily achieved scale industrial production, and there is good economic benefit, environmental protection benefit and good society Benefit.
To achieve the above object, the present invention employs the following technical solutions：
A kind of manufacture method of safety lithium ion cell negative plate, its step is：
The first step is by negative pole pole active substance:Cathode conductive agent presses 1:0.002～1:0.01 mass ratio, ball milling mixing 0.5～3 hour, obtain negative electrode active material mixture A；By cathode additive agent B according to A:The mass ratio of B is respectively：1:0.001 ～1:0.005 ratio, 0.5～4 hour mix homogeneously of ball milling, make negative electrode active material mixture C；
Second step will account for the first step and obtain negative electrode active material mixture C (once referred to as：C) the carboxymethyl of quality 1～5% Sodium cellulosate (english abbreviation：CMC, hereinafter referred to as CMC) it is configured to mass percent concentration for 0.5～6.0% aqueous solution with water, 30～45 DEG C of constant temperature, vacuum (vacuum is less than 0.1MPa, as follows, slightly) stir 0.5～3 hour, and point 3～5 additions account for C matter Bonding agent butadiene-styrene rubber powder (i.e. SB, the english abbreviation of amount 2～10%：SBR, hereinafter referred to as SBR), it is simultaneously introduced the N-methyl pyrrolidinone solvent (letter below accounting for sodium carboxymethyl cellulose (CMC) the solution water yield 1～5% Claim：NMP), 30 DEG C～45 DEG C constant temperature, vacuum stirring 0.5～3 hour, stir into solvent sizing material D；
The negative electrode mix C that the first step obtains is divided 3～5 times and is added in solvent sizing material D by the 3rd step, controls negative pole mixing The mass ratio of thing C amount of solid and water is 650:Between 1000～1200, vacuum stirring prepares cathode size, suitably increases (note：Control The amount of the scope in regulation for the slurry viscosity processed, the 3～8% of about reserved total Water, as follows, slightly) water yield, adjust, control slurry Viscosity, in 1800～3200cps (± 55～65cps, No. 25 rotors, as follows, summaries) scope, vacuum stirring 2～8 hours, obtains Negative electrode active material slurry E；
4th step, with 10～20 μm of Copper Foil for collector F, the slurry one side that obtain the 3rd step or two-sided batch (-type) It is coated on collector, length in reserve is the collector (be not coated by cathode size, as follows, slightly) of 15～45cm, through 75～ 125 DEG C of dryings, control surface density in 10.0～24.5mg/cm2, through rolling to roller, control compacted density 1.35～ 1.85g/cm3, 65～200 μm of pole piece thickness；Through bean noodles, cutting, spot welding lug, adhering polar ear adhesive belt.
A kind of safe lithium ion power battery cathode piece is it is simply that be fabricated by according to as above step.
In order to the present invention is better achieved, described negative electrode active material (refers to for graphite/absorbent charcoal composite material：Figure 4).
Described cathode conductive agent is Super-P, i.e. superfine graphite or super white carbon black or acetylene black, and particle diameter is about 30nm's The mixture of the mass ratioes such as one of graphite or two kinds is (hereinafter referred to as：SP).
Described cathode additive agent be one of Graphene or CNT or two kinds etc. mass ratio mixing.
Described water is deionized water or pure water or one of redistilled water or distilled water.
By manufactured negative plate with mate anode slice of lithium ion battery (capacity be more than negative plate capacity about 10%, Referred to as " positive plate of coupling ", as follows), it is wound into square electric according to respectively negative pole, barrier film, positive pole order from top to bottom Core, then through operations such as vacuum bakeout, injection electrolyte, sealings, manufacture capacity is 1.0 or 2.5 or 5.0Ah lithium-ion electrics Pond, under the conditions of 2C or 10C or 60C multiplying power, the restriction voltage 4.2～4.30V that charges, the charge and discharge circulation life of test battery, Highest discharge capacity, circulation volume conservation rate, internal resistance (be full electricity state under measure averaged static internal resistance, referred to as " internal resistance ", with The performance such as similarly hereinafter), in full electricity state (open-circuit voltage：4.15～4.25V) under test heavy impact test, the safety such as puncture test Energy.
The present invention compared with prior art, has the advantage that and beneficial effect：
1st, a kind of safe lithium ion power battery cathode piece that presently disclosed techniques manufactures, the negative electrode active material being adopted Matter be graphite/absorbent charcoal composite material (referring to Figure of description 2) because this material not only heat stability is good, charge and discharge cycles Process performance is stable, and between 0.1～15 μm, the pole piece have preferable processing characteristics, manufacturing has preferably particle size range Fillibility and higher packed density, increased volume and capacity ratio and the energy density per unit volume of electrode；This composite has simultaneously Fabulous lithium ion is embedding, de- performance, increased the specific discharge capacity of negative pole, the electric discharge further increasing lithium ion battery is held Amount, volume and capacity ratio and volumetric specific power.
2nd, a kind of safe lithium ion power battery cathode piece that presently disclosed techniques manufactures, the negative electrode active material being adopted Matter is graphite/absorbent charcoal composite material, not only heat stability is good, charge and discharge cycles process performance is stable, lithium ion is embedding for this material, De- performance, and this negative active core-shell material has fabulous electrolyte absorption, Penetration Signature, in the electric discharge specific volume increasing negative pole Amount, while the discharge capacity of lithium ion battery, volume and capacity ratio and volumetric specific power so that the lithium being assembled by this pole piece from Sub- electrokinetic cell not only has excellent charge-discharge performance, and has higher security performance；Heavy impact test is not quick-fried Combustion, all qualified.
3rd, a kind of safe lithium ion power battery cathode piece that presently disclosed techniques manufactures, the negative electrode active material being adopted Matter is graphite/absorbent charcoal composite material, and this material has excellent electric conductivity in itself, is simultaneously used compared with conventional lithium ion battery The conductive agents such as super white carbon black that negative pole technique is less, that electric conductivity is good, superior graphite, have excellent electrochemistry cyclicity Can be with good high-rate charge-discharge capability.Under 2C, 10C and 60C charge-discharge mechanism, charge and discharge cycles service life (charge and discharge Electric circulation volume conservation rate is less than or equal to charge and discharge cycles number of times during the 75% of nominal capacity value, i.e. " all " numbers of circulation) minimum It is respectively 1251 weeks, 864 weeks and 625 weeks, highest cycle life respectively reaches 1686 weeks, 1208 weeks and 729 weeks；2C charge-discharge machine Make the 500th cyclic discharge capacity conservation rate average out to 98.5%, be up to 99.2%, the 1000th time cyclic discharge capacity keeps Rate average out to 96.8%, the 300th cyclic discharge capacity conservation rate average out to of up to 98.8%, 10C charge-discharge mechanism 96.1%th, it is up to 97.1%, the 800th cyclic discharge capacity conservation rate average out to 93.9%, up to 95.4%, 60C 300th cyclic discharge capacity conservation rate average out to 93.8% under charge-discharge mechanism, it is up to 95.7%, the 500th circulation is put Capacitance conservation rate average out to 91.8%, up to 93.5%, average specific comparative example 11 capability retention is high respectively 9.3% and 16.8% (2C refers to：Book table 1, table 2 and each embodiment).
4th, a kind of safe lithium ion power battery cathode piece that presently disclosed techniques manufactures, the negative electrode active material being adopted Matter (refers to for graphite/absorbent charcoal composite material：Figure of description 1～accompanying drawing 4) (refer to existing business Delanium：Explanation Book accompanying drawing 5) negative electrode active material compares, because the not only higher specific discharge capacity of this material, charge and discharge cycles process performance Stable, simultaneously as with the addition of thering is that good lithium ion is embedding, the lithium ion battery negative such as Tudor Graphene, CNT adds Plus agent, effectively increasing lithium ion battery charge-discharge performance, itself also having preferable electric conductivity hence it is evident that reducing manufactured Internal resistance (the usually 20～32m Ω of the lithium ion battery internal resistance manufactured by general prior art, and skill of the present invention of lithium ion battery The internal resistance of the lithium ion battery manufactured by art, between 15.7～16.9m Ω, refers to：Table 2, Fig. 8), increase efficiency for charge-discharge Meanwhile, lithium ion battery high magnification, high rate during charging-discharging and good cycle performance are more enhanced；In 60C charge-discharge machine Under system, the capacity that the safe lithium ion power battery cathode piece prepared by the technology of the present invention is assembled is 1.0,2.5 and 5.0Ah Takeup type rectangular lithium ion battery, 300 times and above charge and discharge cycles capability retention all (refer to more than 90%：Each reality Apply example and table 1, table 2, Fig. 6～Figure 12).
5th, a kind of safety lithium ion cell negative plate that the technology of the present invention manufactures, difficult not increasing raw material manufacturing technology On the premise of degree, the manufacturing cost substantially increasing existing raw material and raw material cost taken by themselves, the new additive agent quoted and modification Active material etc. be all conventional, be easy to get, environment friendly material, intrinsic lithium ion battery will not be changed：Performance While excellent, environmental friendliness, excellent electrochemical performance maximum characteristic, application the technology of the present invention applies new negative electrode active material Matter graphite/absorbent charcoal material, (refers to because this material has higher porosity：Figure of description 4), not only have preferably Lithium-ion embeding and abjection performance, also have and have preferable characterization of adsorption to electrolyte, considerably increase the effective suction to electrolyte Attached amount, reduces the internal resistance of active substance, simultaneously so that electrolyte is more difficult is gasified, greatly under higher temperature and external impacts Enhance greatly the security performance of assembled lithium-ion-power cell, under the extreme case such as puncture test, heavy impact test Do not explode and (referring to description table 2 and accompanying drawing 13～accompanying drawing 15) on fire.
6th, a kind of " safety lithium ion cell negative plate " manufacture of the present invention simplifies existing conventional lithium ion battery and bears Pole manufactures typical process flow, and present invention process is relatively easy, is effectively shortened production time, improve production efficiency；Electrode Operation principle is clear, and low production cost is both suitable for manufacturing the lithium ion battery power supply of the general digital electrical apparatus of various models, It is also applied for manufacturing the lithium-ion-power cell of high power charging-discharging, manufacturing process efficiently, and need not carry out to existing equipment appointing What special transformation or renewal, manufacture process, cycle is short, energy consumption is low, is advantageously implemented intensive scale industrial production, has good Good economic benefit and green, environmental benefit, are also beneficial to safe social benefit.
Brief description
The section view organigram of the anode plate for lithium ionic cell that Fig. 1 manufactures for exemplary embodiments of the present invention
Fig. 2 is the lithium ion battery Double-pole lug of exemplary embodiments manufacture of the present invention, double spread negative plate D structure shows It is intended to
Fig. 3 be exemplary embodiments of the present invention manufactured by lithium ion battery monopole ear, single spreading negative plate D structure Schematic diagram
The SEM photograph (amplifying 5K times) of negative electrode active material graphite/absorbent charcoal composite material that Fig. 4 adopts for the present invention
Fig. 5 is the SEM photograph (amplifying 5K times) of the negative electrode active material graphite material that comparative example 11 of the present invention adopts
Fig. 6 is the lithium ion battery 2C rate charge-discharge curve of the negative plate assembling that embodiment 2 manufactures
Fig. 7 is the lithium ion battery 10C charging and discharging curve of the negative plate assembling that embodiment 5 manufactures
Fig. 8 is embodiment 6,100 circulation times of lithium ion battery 2C discharge and recharge of 11 negative plate assemblings, internal resistance comparison diagram
Fig. 9 is that 500 discharge and recharges of lithium ion battery 60C multiplying power of embodiment 6,7,11 negative plate assembling follow correlation curve
Figure 10 is the lithium ion battery 10C charge and discharge cycles efficiency chart of the negative plate assembling that embodiment 8,11 manufactures
Figure 11 is the lithium ion battery 60C charging and discharging curve of the negative plate assembling that embodiment 9,11 manufactures
Figure 12 is the lithium ion battery 60C charge-discharge performance figure of the negative plate assembling that embodiment 10 manufactures
Figure 13 is the lithium ion battery heavy impact safety test photo of the negative plate assembling that embodiment 3,4 manufactures
Figure 14 is the lithium ion battery heavy impact safety test photo of the negative plate assembling that embodiment 6,9 manufactures
Figure 15 is the lithium-ion electric cisternal puncture safety test photo of the negative plate assembling manufactured by exemplary embodiments
Specific embodiment
Embodiment 1:
A kind of manufacture method of safety lithium ion cell negative plate, comprises the steps and process conditions：
The first step is by negative pole pole active substance graphite/absorbent charcoal composite material:SP presses 1:0.002 mass ratio, ball milling mixes Close 0.5 hour, obtain negative electrode active material mixture A；By cathode additive agent Graphene B；According to A:The mass ratio of B is 1: 0.005 ratio, 4 hours mix homogeneously of ball milling, make negative electrode active material mixture C；
It is water-soluble for 0.5% that the CMC distilled water accounting for mixture C quality 1% is configured to mass percent concentration by second step Liquid, 30 DEG C of constant temperature, vacuum stirring 0.5 hour, point add the SBR accounting for C material mass 2% 3 or 4 or 5 times, be simultaneously introduced and account for CMC The nmp solvent of solution water yield quality 1%, 30 DEG C of constant temperature, vacuum stirring 0.5 hour, stir into solvent sizing material D；
C is divided 3 times and is added in D by the 3rd step, controls the mass ratio of C amount of solid and water 650:1000, vacuum stirring system Standby cathode size, suitably increase the water yield, adjusts, controls slurry viscosity in 1800cps, and vacuum stirring 2 hours obtains negative pole Active material slurry E；
With 10 μm of Copper Foil for collector F, the two-sided batch (-type) of slurry E that the 3rd step is obtained is coated on collector to 4th step On, length in reserve is the collector of 15cm, through 125 DEG C of dryings, controls surface density 10mg/cm2, through to roller roll, control Compacted density 1.85g/cm3, 65 μm of pole piece thickness；Through bean noodles, cutting, spot welding lug, adhering polar ear adhesive belt.
A kind of safe lithium ion power battery cathode piece is it is simply that be fabricated by according to as above step.
Manufactured negative plate (is referred to：Fig. 1～Fig. 3) with the positive plate mating, according to from top to bottom be respectively negative pole, Barrier film, positive pole order are wound into square electric cell, then through operations such as vacuum bakeout, injection electrolyte, sealings, manufacturing capacity is 1.0 or 2.5 or 5.0Ah lithium ion batteries, under the conditions of 2C or 10C multiplying power, the restriction voltage 4.2～4.30V that charges, test The performances such as the charge and discharge circulation life of battery, highest discharge capacity, circulation volume conservation rate, internal resistance, in full electricity state (open circuit electricity Pressure：4.15～4.25V) under test heavy impact test, the security performance such as puncture test.Test result shows：2C and 10C charge and discharge The discharge cycles life-span that electricity fills under mechanism is respectively 1251 weeks, 876 weeks；1.0Ah battery highest discharge capacity is 1001.9mAh (2C), 2.5Ah battery highest discharge capacity is 2495mAh (10C)；2C multiplying power, the 500th time circulation volume conservation rate is 98.6%th, the 1000th charge and discharge cycles capability retention is 95.2%；10C multiplying power, the 300th circulation volume conservation rate 95.7%th, the 800th charge and discharge cycles capability retention is 94.0%；Internal resistance is 16.7m Ω；Heavy impact test no short circuit, Non-detonating；Puncture test no short circuit, non-detonating (refer to：Table 1, table 2, Figure 15).
Embodiment 2:
A kind of manufacture method of safety lithium ion cell negative plate, comprises the steps and process conditions：
The first step is by negative pole pole active substance graphite/absorbent charcoal composite material:SP presses 1:0.004 mass ratio, ball milling mixes Close 1 hour, obtain negative electrode active material mixture A；By CNT B according to A:The mass ratio of B is respectively：1:0.004 ratio Example, 1 hour mix homogeneously of ball milling, make negative electrode active material mixture C；
It is 1% aqueous solution that the CMC redistilled water accounting for C mass 2% is configured to mass percent concentration by second step, 35 DEG C constant temperature, vacuum stirring 1 hour, point add the SBR accounting for C mass 4% 3 or 4 or 5 times, are simultaneously introduced and account for the CMC solution water yield 2% NMP, 35 DEG C of constant temperature, vacuum stirring 1 hour, stir into solvent sizing material D；
The C that the first step obtains is divided 3 or 4 or 5 times and is added in solvent sizing material D by the 3rd step, controls negative electrode mix C solid Amount and the mass ratio of water are 700:1050, vacuum stirring prepares cathode size, suitably increases the water yield, adjusts, controls slurry viscosity In 2200cps about, vacuum stirring 4 hours, obtain negative electrode active material slurry E；
4th step, with 15 μm of Copper Foil for collector F, the slurry E one side batch (-type) that the 3rd step is obtained is coated on afflux On body, length in reserve is the collector of 20cm, through 105 DEG C of dryings, controls surface density 12.5mg/cm2, through to roller roll, Control compacted density 1.75g/cm3, 85 μm of pole piece thickness；Through bean noodles, cutting, spot welding lug, adhering polar ear adhesive belt.
A kind of safe lithium ion power battery cathode piece is it is simply that be fabricated by according to as above step.
Manufactured negative plate (is referred to：Fig. 1～Fig. 3) with the positive plate mating, according to from top to bottom be respectively negative pole, Barrier film, positive pole order are wound into square electric cell, then through operations such as vacuum bakeout, injection electrolyte, sealings, manufacturing capacity is 1.0 or 2.5 or 5.0Ah lithium ion batteries, under the conditions of 2C or 10C multiplying power, the restriction voltage 4.2～4.30V that charges, test The performances such as the charge and discharge circulation life of battery, highest discharge capacity, circulation volume conservation rate, internal resistance, in full electricity state (open circuit electricity Pressure：4.15～4.25V) under test heavy impact test, the security performance such as puncture test.Test result shows：2C and 10C charge and discharge The discharge cycles life-span that electricity fills under mechanism is respectively 1294 weeks, 894 weeks；1.0Ah battery highest discharge capacity is 1001.9mAh (2C), 2.5Ah battery highest discharge capacity is 2495mAh (10C)；2C multiplying power, the 500th time circulation volume conservation rate is 99.1%th, the 1000th charge and discharge cycles capability retention is 98.0%；10C multiplying power, the 300th circulation volume conservation rate 96.7%th, the 800th charge and discharge cycles capability retention is 95.1%；Internal resistance is 16.6m Ω；In heavy impact test minority has Short circuit, non-detonating；Puncture test no short circuit, non-detonating (refer to：Table 1, table 2, Fig. 6, Figure 15).
Embodiment 3:
A kind of manufacture method of safety lithium ion cell negative plate, comprises the steps and process conditions：
The first step is by graphite/absorbent charcoal composite material:SP presses 1:0.006 mass ratio, ball milling mixing 1.5 hours, obtain Negative electrode active material mixture A；By the mixture B of the Graphene waiting mass ratio to mix and CNT according to A:The mass ratio of B For：1:0.003 ratio, 2 hours mix homogeneously of ball milling, make negative electrode active material mixture C；
Second step obtains the CMC of C mass 3% by accounting for the first step, and being configured to mass percent concentration with pure water is 2.0% Aqueous solution, 40 DEG C of constant temperature, vacuum stirring 2 hours, point add the SBR accounting for C mass 6% 3 or 4 or 5 times, be simultaneously introduced that to account for CMC molten The NMP of the liquid water yield 3%, 40 DEG C of constant temperature, vacuum stirring, 3 hours, stir into solvent sizing material D；
The C that the first step obtains is divided 3 or 4 or 5 times and is added in solvent sizing material D by the 3rd step, controls negative electrode mix C solid Amount and the mass ratio of water are 650:1100, vacuum stirring prepares cathode size, suitably increases the water yield, adjusts, controls slurry viscosity In 2600cps about, vacuum stirring 5 hours, obtain negative electrode active material slurry E；
4th step, with 16 μm of Copper Foil for collector F, the two-sided batch (-type) of slurry E that the 3rd step is obtained is coated on afflux On body, length in reserve is the collector of 25cm, through 95 DEG C of dryings, controls surface density 15mg/cm2, through to roller roll, control Compacted density 1.65g/cm3, 105 μm of pole piece thickness；Through bean noodles, cutting, spot welding lug, adhering polar ear adhesive belt.
A kind of safe lithium ion power battery cathode piece is it is simply that be fabricated by according to as above step.
Manufactured negative plate (is referred to：Fig. 1～Fig. 3) with the positive plate mating, according to from top to bottom be respectively negative pole, Barrier film, positive pole order are wound into square electric cell, then through operations such as vacuum bakeout, injection electrolyte, sealings, manufacturing capacity is 1.0 or 2.5 or 5.0Ah lithium ion batteries, under the conditions of 2C or 10C or 60C multiplying power, the restriction voltage 4.2～4.30V that charges, The performances such as the charge and discharge circulation life of test battery, highest discharge capacity, circulation volume conservation rate, internal resistance, in full electricity state (open circuit Voltage：The security performance such as test heavy impact test, puncture test under 4.25V).Test result shows：2C, 10C and 60C charge and discharge The discharge cycles life-span that electricity fills under mechanism is respectively 1346 weeks, 1012 weeks and 632 weeks；1.0Ah battery highest discharge capacity is 1000mAh (2C), 2.5Ah battery highest discharge capacity is 2488mAh (10C)；1.0Ah battery highest discharge capacity is 963mAh (60C)；2C multiplying power, the 500th time circulation volume conservation rate for the 97.5%, the 1000th charge and discharge cycles capability retention is 95.9%；10C multiplying power, the 300th time circulation volume conservation rate 95.5%, the 800th charge and discharge cycles capability retention are 93.8%；60C multiplying power, the 300th time circulation volume conservation rate for the 92.9%, the 500th charge and discharge cycles capability retention is 91.2%；Internal resistance is 15.9m Ω；Heavy impact test no short circuit, non-detonating；Puncture test minority has internal short-circuit, and non-detonating is (in detail See：Table 1, table 2, Figure 13, Figure 15).
Embodiment 4:
A kind of manufacture method of safety lithium ion cell negative plate, comprises the steps and process conditions：
The first step is by negative pole pole active substance:Conductive agent presses 1:0.008 mass ratio, ball milling mixing 2 hours, obtain negative pole Active material admixture A；By Graphene B according to A:The mass ratio of B is 1:0.002 ratio, 3 hours mix homogeneously of ball milling, system Become negative electrode active material mixture C；
The CMC deionized water accounting for the first step and obtaining C mass 4% is configured to mass percent concentration by second step 4.0% aqueous solution, 45 DEG C of constant temperature, vacuum, stirring 3 hours, point add the SBR accounting for C mass 8% 3～5 times, be simultaneously introduced and account for CMC The NMP of the solution water yield 4%, 45 DEG C of constant temperature, vacuum stirring 2 hours, stir into solvent sizing material D；
The C that the first step obtains is divided 3～5 times and is added in solvent sizing material D by the 3rd step, controls negative electrode mix A amount of solid With the mass ratio of water 650:Between 1150, vacuum stirring prepares cathode size, suitably increases (note：Control slurry viscosity on rule The amount of fixed scope, as follows, slightly) water yield, adjust, control slurry viscosity in 3000cps, vacuum stirring 6 hours, obtain Negative electrode active material slurry E；
4th step, with 18 μm of Copper Foil for collector F, the slurry one side that obtain the 3rd step or two-sided batch (-type) coating On collector, length in reserve is the collector of 35cm, through 85 DEG C of dryings, controls surface density 17.5mg/cm2, through to roller Rolling, controls compacted density 1.55g/cm3, 130 μm of pole piece thickness；Through bean noodles, cutting, spot welding lug, adhering polar ear adhesive belt.
A kind of safe lithium ion power battery cathode piece is it is simply that be fabricated by according to as above step.
Manufactured negative plate (is referred to：Fig. 1～Fig. 3) with the positive plate mating, according to from top to bottom be respectively negative pole, Barrier film, positive pole order are wound into square electric cell, then through operations such as vacuum bakeout, injection electrolyte, sealings, manufacturing capacity is 1.0 or 2.5Ah lithium ion batteries, under the conditions of 10C or 60C multiplying power, the restriction voltage 4.2～4.30V that charges, test filling of battery The performances such as discharge cycles life-span, highest discharge capacity, circulation volume conservation rate, internal resistance, in full electricity state (open-circuit voltage：4.25V) The security performances such as lower test heavy impact test, puncture test.Test result shows：Electric discharge under 10C and 60C charge-discharge mechanism Cycle life is respectively 956 weeks, 685 weeks；2.5Ah battery highest discharge capacity is 2483mAh (10C)；1.0Ah battery highest Discharge capacity is 978mAh (60C)；10C multiplying power, the 300th time circulation volume conservation rate 96.9%, the 800th charge and discharge cycles are held Amount conservation rate is 94.2%；60C multiplying power, the 300th circulation volume conservation rate is the 91.6%, the 500th charge and discharge cycles capacity Conservation rate is 90.8%；Internal resistance is 16.3m Ω；Heavy impact tests non-detonating, and minority has internal short-circuit；Puncture test no short circuit, Non-detonating (refers to：Table 1, table 2, Figure 13, Figure 15).
Embodiment 5:
A kind of manufacture method of safety lithium ion cell negative plate, comprises the steps and process conditions：
The first step is by negative pole pole active substance:Conductive agent presses 1:0.01 mass ratio, ball milling mixing 3 hours, obtain negative pole Active material admixture A；By CNT B according to A:The mass ratio of B is 1:0.005 ratio, 4 hours mix homogeneously of ball milling, Make negative electrode active material mixture C；
The CMC redistilled water accounting for the quality 5% that the first step obtains C is configured to mass percent concentration by second step 6.0% aqueous solution, 45 DEG C of constant temperature, vacuum stirring 3 hours, point add the SBR accounting for C mass 10% 3～5 times, be simultaneously introduced and account for CMC The NMP of solution water 5%, 45 DEG C of constant temperature, vacuum stirring 3 hours, stir into solvent sizing material D；
The mixture C that the first step obtains is divided 3～5 times and is added in solvent sizing material D by the 3rd step, controls negative electrode mix A The mass ratio of amount of solid and water is 650:1200, vacuum stirring prepares cathode size, suitably increases the water yield, adjusts, controls slurry Viscosity in 3200cps, vacuum stirring 8 hours, obtain negative electrode active material slurry E；
4th step, with 20 μm of Copper Foil for collector F, the slurry one side that obtain the 3rd step or two-sided batch (-type) coating On collector, length in reserve is the collector of 45cm, through 75 DEG C of dryings, controls surface density 20.0mg/cm2, through to roller Rolling, controls compacted density 1.45g/cm3, 165 μm of pole piece thickness；Through bean noodles, cutting, spot welding lug, adhering polar ear adhesive belt.
A kind of safe lithium ion power battery cathode piece is it is simply that be fabricated by according to as above step.
Manufactured negative plate (is referred to：Fig. 1～Fig. 3) with the positive plate mating, according to from top to bottom be respectively negative pole, Barrier film, positive pole order are wound into square electric cell, then through operations such as vacuum bakeout, injection electrolyte, sealings, manufacturing capacity is 2.5 or 5.0Ah lithium ion batteries, under the conditions of 10C or 60C multiplying power, the restriction voltage 4.2～4.30V that charges, test filling of battery The performances such as discharge cycles life-span, highest discharge capacity, circulation volume conservation rate, internal resistance, in full electricity state (open-circuit voltage：4.15V) The security performances such as lower test heavy impact test, puncture test.Test result shows：Electric discharge under 10C and 60C charge-discharge mechanism Cycle life is respectively 892 weeks, 701 weeks；2.5Ah battery highest discharge capacity is 2487mAh (10C)；5.0Ah battery highest Discharge capacity is 4957mAh (60C)；10C multiplying power, the 300th circulation volume conservation rate 95.2%, the 800th charge and discharge cycles Capability retention is 92.6%；60C multiplying power, the 300th circulation volume conservation rate is that the 93.8%, the 500th charge and discharge cycles are held Amount conservation rate is 92.6%；Internal resistance is 16.9m Ω；Heavy impact test, puncture test all no short circuit, non-detonatings (refer to：Table 1, Table 2, Fig. 7, Figure 15).
Embodiment 6:
A kind of manufacture method of safety lithium ion cell negative plate, comprises the steps and process conditions：
The first step is by negative pole pole active substance graphite/absorbent charcoal composite material:SP presses 1:0.002 mass ratio, ball milling mixes Close 3 hours, obtain negative electrode active material mixture A；Graphene-carbon nano tube mixing by the mixing of the mass ratioes such as cathode additive agent Thing B；According to A:The mass ratio of B is 1:0.002 ratio, 0.5 hour mix homogeneously of ball milling, make negative electrode active material mixture C；
It is water-soluble for 2% that the CMC deionized water accounting for mixture C quality 5% is configured to mass percent concentration by second step Liquid, 30 DEG C of constant temperature, vacuum stirring 2 hours, point add the SBR accounting for C material mass 3% 3～5 times, be simultaneously introduced and account for CMC solution water The nmp solvent of amount 1%, 30 DEG C of constant temperature, vacuum stirring 0.5 hour, stir into solvent sizing material D；
C is divided 3 times and is added in D by the 3rd step, controls the mass ratio of C amount of solid and water 650:1200, vacuum stirring system Standby cathode size, suitably increase amount of deionized water, adjusts, controls slurry viscosity in 1800cps, and vacuum stirring 2 hours obtains To negative electrode active material slurry E；
With 16 μm of Copper Foil for collector F, the two-sided batch (-type) of slurry E that the 3rd step is obtained is coated on collector to 4th step On, length in reserve is the collector of 45cm, through 85 DEG C of dryings, controls surface density 22.5mg/cm2, through to roller roll, control Compacted density 1.35g/cm3, 185 μm of pole piece thickness；Through bean noodles, cutting, spot welding lug, adhering polar ear adhesive belt.
A kind of safe lithium ion power battery cathode piece is it is simply that be fabricated by according to as above step.
Manufactured negative plate (is referred to：Fig. 1～Fig. 3) with the positive plate mating, according to from top to bottom be respectively negative pole, Barrier film, positive pole order are wound into square electric cell, then through operations such as vacuum bakeout, injection electrolyte, sealings, manufacturing capacity is 1.0 or 2.5 or 5.0Ah lithium ion batteries, under the conditions of 2C or 10C or 60C multiplying power, the restriction voltage 4.2～4.30V that charges, survey The performances such as the charge and discharge circulation life of examination battery, highest discharge capacity, circulation volume conservation rate, internal resistance, in full electricity state (open circuit electricity Pressure：4.15V, 4.25V) under test heavy impact test, the security performance such as puncture test.Test result shows：2C, 10C and 60C The discharge cycles life-span under charge-discharge mechanism is respectively 1686 weeks, 1208 weeks, 729 weeks；1.0Ah battery highest discharge capacity is 1151.1mAh(2C)；2.5Ah battery highest discharge capacity is 2509mAh (10C)；1.0Ah battery highest discharge capacity is 1107mAh(60C)；5.0Ah battery highest discharge capacity is 4989mAh (60C)；2C multiplying power, the 500th circulation volume conservation rate 99.2%th, the 1000th charge and discharge cycles capability retention is 98.8%；10C multiplying power, the 300th circulation volume conservation rate 97.1%th, the 800th charge and discharge cycles capability retention is 95.4%；60C multiplying power, the 300th time circulation volume conservation rate is 95.7%th, the 500th charge and discharge cycles capability retention is 93.5%；Internal resistance is 15.8m Ω；Heavy impact test, puncture examination Test all no short circuit, non-detonatings (to refer to：Table 1, table 2, Fig. 8, Fig. 9, Figure 14, Figure 15).
Embodiment 7:
A kind of manufacture method of safety lithium ion cell negative plate, comprises the steps and process conditions：
The first step is by negative pole pole active substance graphite/absorbent charcoal composite material:SP presses 1:0.006 mass ratio, ball milling mixes Close 1 hour, obtain negative electrode active material mixture A；By CNT B according to A:The mass ratio of B is respectively：1:0.003 ratio Example, 2 hours mix homogeneously of ball milling, make negative electrode active material mixture C；
It is 1% aqueous solution that the CMC deionized water accounting for C mass 2% is configured to mass percent concentration by second step, 35 DEG C Constant temperature, vacuum stirring 1 hour, point 3～5 additions account for the SBR of C mass 4%, are simultaneously introduced the NMP accounting for the CMC solution water yield 2%, 35 DEG C of constant temperature, vacuum stirring 1 hour, stir into solvent sizing material D；
The C that the first step obtains is divided 3～5 times and is added in solvent sizing material D by the 3rd step, controls negative electrode mix C amount of solid With the mass ratio of water 650:1150, vacuum stirring prepares cathode size, suitably increases amount of deionized water, adjusts, controls slurry Viscosity in 2200cps, vacuum stirring 4 hours, obtain negative electrode active material slurry E；
4th step, with 12 μm of Copper Foil for collector F, the slurry E one side batch (-type) that the 3rd step is obtained is coated on afflux On body, length in reserve is the collector of 20cm, through 105 DEG C of dryings, controls surface density 24.5mg/cm2, through to roller roll, Control compacted density 1.85g/cm3, 145 μm of pole piece thickness；Through bean noodles, cutting, spot welding lug, adhering polar ear adhesive belt.
A kind of safe lithium ion power battery cathode piece is it is simply that be fabricated by according to as above step.
Manufactured negative plate (is referred to：Fig. 1～Fig. 3) with the positive plate mating, according to from top to bottom be respectively negative pole, Barrier film, positive pole order are wound into square electric cell, then through operations such as vacuum bakeout, injection electrolyte, sealings, manufacturing capacity is 1.0 or 2.5 or 5.0Ah lithium ion batteries, under the conditions of 2C or 10C or 60C multiplying power, the restriction voltage 4.2～4.30V that charges, survey The performances such as the charge and discharge circulation life of examination battery, highest discharge capacity, circulation volume conservation rate, internal resistance, in full electricity state (open circuit electricity Pressure：4.15V or 4.25V) under test heavy impact test, the security performance such as puncture test.Test result shows：2C, 10C and The discharge cycles life-span under 60C charge-discharge mechanism is respectively 1273 weeks, 864 weeks, 625 weeks；1.0Ah battery highest discharge capacity For 998mAh (2C)；2.5Ah battery highest discharge capacity is 2513mAh (10C)；1.0Ah battery highest discharge capacity is 1017mAh(60C)；2C multiplying power, the 500th circulation volume conservation rate 98.5%, the 1000th charge and discharge cycles capability retention For 96.5%；10C multiplying power, the 300th time circulation volume conservation rate 95.6%, the 800th charge and discharge cycles capability retention are 93.1%；60C multiplying power, the 300th time circulation volume conservation rate for the 94.2%, the 500th charge and discharge cycles capability retention is 92.2%；Internal resistance is 16.4m Ω；Heavy impact test, puncture test all no short circuit, non-detonatings (refer to：Table 1, table 2, Fig. 9, figure 15).
Embodiment 8:
A kind of manufacture method of safety lithium ion cell negative plate, comprises the steps and process conditions：
The first step is by graphite/absorbent charcoal composite material:SP presses 1:0.008 mass ratio, ball milling mixing 1.5 hours, obtain Negative electrode active material mixture A；By the mixture B of the Graphene waiting mass ratio to mix and CNT according to A:The mass ratio of B For：1:0.004 ratio, 3 hours mix homogeneously of ball milling, make negative electrode active material mixture C；
Second step obtains the CMC of C mass 3% by accounting for the first step, is configured to mass percent concentration with pure water and is 2.0% aqueous solution, 40 DEG C of constant temperature, vacuum stirring 2 hours, point add the SBR accounting for C mass 6% 3～5 times, be simultaneously introduced and account for CMC The NMP of the solution water yield 3%, 40 DEG C of constant temperature, vacuum stirring, 3 hours, stir into solvent sizing material D；
The C that the first step obtains is divided 3～5 times and is added in solvent sizing material D by the 3rd step, controls negative electrode mix C amount of solid With the mass ratio of water 650:1050, vacuum stirring prepares cathode size, suitably increases the water yield, adjusts, controls slurry viscosity to exist 3000cps about, vacuum stirring 5 hours, obtain negative electrode active material slurry E；
4th step, with 16 μm of Copper Foil for collector F, the two-sided batch (-type) of slurry E that the 3rd step is obtained is coated on afflux On body, length in reserve is the collector of 25cm, through 95 DEG C of dryings, controls surface density 22.5mg/cm2, through to roller roll, control Compacted density 1.45g/cm processed3, 170 μm of pole piece thickness；Through bean noodles, cutting, spot welding lug, adhering polar ear adhesive belt.
A kind of safe lithium ion power battery cathode piece is it is simply that be fabricated by according to as above step.
Manufactured negative plate (is referred to：Fig. 1～Fig. 3) with the positive plate mating, according to from top to bottom be respectively negative pole, Barrier film, positive pole order are wound into square electric cell, then through operations such as vacuum bakeout, injection electrolyte, sealings, manufacturing capacity is 1.0 or 2.5Ah lithium ion batteries, under the conditions of 2C or 10C multiplying power, the restriction voltage 4.2～4.30V that charges, test filling of battery The performances such as discharge cycles life-span, highest discharge capacity, circulation volume conservation rate, internal resistance, in full electricity state (open-circuit voltage：4.15～ The security performance such as test heavy impact test, puncture test under 4.25V).Test result shows：Mechanism is filled in 2C and 10C discharge and recharge Under the discharge cycles life-span respectively be 1469 weeks, 1093 weeks；1.0Ah battery highest discharge capacity is 995.8mAh (2C), 2.5Ah battery highest discharge capacity is 2492mAh (10C)；2C multiplying power, the 500th circulation volume conservation rate be 98.9%, the 1000 times charge and discharge cycles capability retention is 96.8%；10C multiplying power, the 300th circulation volume conservation rate the 95.4%, the 800th Secondary charge and discharge cycles capability retention is 93.7%；Internal resistance is 15.7m Ω；Heavy impact test minority has internal short-circuit, non-detonating； Puncture test no short circuit, non-detonating (refer to：Table 1, table 2, Figure 10, Figure 15).
Embodiment 9:
A kind of manufacture method of safety lithium ion cell negative plate, comprises the steps and process conditions：
The first step is by negative pole pole active substance:Conductive agent presses 1:0.01 mass ratio, ball milling mixing 3 hours, obtain negative pole Active material admixture A；By Graphene B according to A:The mass ratio of B is 1:0.005 ratio, 4 hours mix homogeneously of ball milling, system Become negative electrode active material mixture C；
The CMC deionized water accounting for the first step and obtaining C mass 4% is configured to mass percent concentration by second step 4.0% aqueous solution, 30 DEG C of constant temperature, vacuum, stirring 3 hours, point add the SBR accounting for C mass 8% 3～5 times, be simultaneously introduced and account for CMC The NMP of the solution water yield 4%, 30 DEG C of constant temperature, vacuum stirring 2 hours, stir into solvent sizing material D；
The C that the first step obtains is divided 3～5 times and is added in solvent sizing material D by the 3rd step, controls negative electrode mix A amount of solid With the mass ratio of water 650:Between 1150, vacuum stirring prepares cathode size, suitably increases the water yield, adjusts, controls slurry to glue Spend in 3200cps about, vacuum stirring 6 hours, obtain negative electrode active material slurry E；
4th step, with 12 μm of Copper Foil for collector F, the slurry one side that obtain the 3rd step or two-sided batch (-type) coating On collector, length in reserve is the collector of 35cm, through 85 DEG C of dryings, controls surface density 10mg/cm2, through to roller roll Pressure, controls compacted density 1.75g/cm3, 60 μm of pole piece thickness；Through bean noodles, cutting, spot welding lug, adhering polar ear adhesive belt.
A kind of safe lithium ion power battery cathode piece is it is simply that be fabricated by according to as above step.
Manufactured negative plate (is referred to：Fig. 1～Fig. 3) with the positive plate mating, according to from top to bottom be respectively negative pole, Barrier film, positive pole order are wound into square electric cell, then through operations such as vacuum bakeout, injection electrolyte, sealings, manufacturing capacity is 2.5 or 5.0Ah lithium ion batteries, under the conditions of 10C or 60C multiplying power, the restriction voltage 4.2～4.30V that charges, test filling of battery The performances such as discharge cycles life-span, highest discharge capacity, circulation volume conservation rate, internal resistance, in full electricity state (open-circuit voltage：4.15V or The security performance such as test heavy impact test, puncture test under 4.25V).Test result shows：Under 10C and 60C charge-discharge mechanism The discharge cycles life-span respectively be 1165 weeks, 697 weeks；2.5Ah battery highest discharge capacity is 2506mAh (10C)；5.0Ah Battery highest discharge capacity is 4975mAh (60C)；10C multiplying power, the 300th circulation volume conservation rate 96.8%, fills for the 800th time Discharge cycles capability retention is 92.2%；60C multiplying power, the 300th circulation volume conservation rate is the 94.5%, the 500th charge and discharge Electric circulation volume conservation rate is 91.1%；Internal resistance is 16.2m Ω；Heavy impact is tested, puncture test is all no short-circuit, non-detonating (refer to：Table 1, table 2, Figure 11, Figure 14, Figure 15).
Embodiment 10:
A kind of manufacture method of safety lithium ion cell negative plate, comprises the steps and process conditions：
The first step is by negative pole pole active substance:Conductive agent presses 1:0.004 mass ratio, ball milling mixing 2 hours, born Pole active material admixture A；By CNT B according to A:The mass ratio of B is 1:0.001 ratio, ball milling mixing in 1 hour is all Even, make negative electrode active material mixture C；
The CMC redistilled water accounting for the quality 5% that the first step obtains C is configured to mass percent concentration by second step For 6.0% aqueous solution, 45 DEG C of constant temperature, vacuum stirring 3 hours, point add the SBR accounting for C mass 10% 3～5 times, be simultaneously introduced and account for The NMP of CMC solution water 5%, 45 DEG C of constant temperature, vacuum stirring 3 hours, stir into solvent sizing material D；
The mixture C that the first step obtains is divided 3～5 times and is added in solvent sizing material D by the 3rd step, controls negative electrode mix A The mass ratio of amount of solid and water is 650:1150, vacuum stirring prepares cathode size, suitably increases the water yield, adjusts, controls slurry Viscosity in 3000cps, vacuum stirring 8 hours, obtain negative electrode active material slurry E；
4th step, with 20 μm of Copper Foil for collector F, the slurry one side that obtain the 3rd step or two-sided batch (-type) coating On collector, length in reserve is the collector of 45cm, through 75 DEG C of dryings, controls surface density 24.5mg/cm2, through to roller Rolling, controls compacted density 1.35g/cm3, 200 μm of pole piece thickness；Through bean noodles, cutting, spot welding lug, adhering polar ear adhesive belt.
A kind of safe lithium ion power battery cathode piece is it is simply that be fabricated by according to as above step.
Manufactured negative plate (is referred to：Fig. 1～Fig. 3) with the positive plate mating, according to from top to bottom be respectively negative pole, Barrier film, positive pole order are wound into square electric cell, then through operations such as vacuum bakeout, injection electrolyte, sealings, manufacturing capacity is 1.0 or 2.5 or 5.0Ah lithium ion batteries, under the conditions of 2C or 10C or 60C multiplying power, the restriction voltage 4.2～4.30V that charges, survey The performances such as the charge and discharge circulation life of examination battery, highest discharge capacity, circulation volume conservation rate, internal resistance, in full electricity state (open circuit electricity Pressure：The security performance such as test heavy impact test, puncture test under 4.25V).Test result shows：2C, 10C and 60C discharge and recharge The discharge cycles life-span under mechanism is respectively 1508 weeks, 1172 weeks, 681 weeks；1.0Ah battery highest discharge capacity is 1075.5mAh(2C)；2.5Ah battery highest discharge capacity is 2514mAh (10C)；5.0Ah battery highest discharge capacity is 4987mAh(60C)；2C multiplying power, the 500th circulation volume conservation rate 97.7%, the 1000th charge and discharge cycles capability retention For 96.8%；10C multiplying power, the 300th time circulation volume conservation rate 96.3%, the 800th charge and discharge cycles capability retention are 95.0%；60C multiplying power, the 300th time circulation volume conservation rate for the 94.2%, the 500th charge and discharge cycles capability retention is 91.7%；Internal resistance is 16.0m Ω；Heavy impact test, puncture test all no short circuit, non-detonatings (refer to：Table 1, table 2, Fig. 9, figure 15).
Comparative example 11:
A kind of manufacture method of safety lithium ion cell negative plate, comprises the steps and process conditions：
The first step is by business negative pole pole active substance graphite:SP presses 1:0.002 mass ratio, ball milling mixing 3 hours, obtain To negative electrode active material mixture A；Graphene-carbon nano tube mixture B by the mixing of the mass ratioes such as cathode additive agent；According to A: The mass ratio of B is 1:0.002 ratio, 0.5 hour mix homogeneously of ball milling, make negative electrode active material mixture C；
It is water-soluble for 2% that the CMC deionized water accounting for mixture C quality 5% is configured to mass percent concentration by second step Liquid, 30 DEG C of constant temperature, vacuum stirring 2 hours, point add the SBR accounting for C material mass 3% 3～5 times, be simultaneously introduced and account for CMC solution water The nmp solvent of amount 1%, 30 DEG C of constant temperature, vacuum stirring 0.5 hour, stir into solvent sizing material D；
C is divided 3 times and is added in D by the 3rd step, controls the mass ratio of C amount of solid and water 650:1200, vacuum stirring system Standby cathode size, suitably increase amount of deionized water, adjusts, controls slurry viscosity in 1800cps, and vacuum stirring 2 hours obtains To negative electrode active material slurry E；
With 16 μm of Copper Foil for collector F, the two-sided batch (-type) of slurry E that the 3rd step is obtained is coated on afflux to 4th step On body, length in reserve is the collector of 45cm, through 85 DEG C of dryings, controls surface density 17.5mg/cm2, through to roller roll, control Compacted density 1.65g/cm processed3, 120 μm of pole piece thickness；Through bean noodles, cutting, spot welding lug, adhering polar ear adhesive belt.
A kind of anode plate for lithium ionic cell is it is simply that be fabricated by according to as above step.
By manufactured negative plate and the positive plate mating, according to being respectively negative pole, barrier film, positive pole sequential volume from top to bottom It is coiled into square electric cell, then through operations such as vacuum bakeout, injection electrolyte, sealings, manufacture capacity is 1.0 or 2.5 or 5.0Ah lithiums Ion battery, under the conditions of 2C or 10C or 60C multiplying power, the restriction voltage 4.2～4.30V that charges, the charge and discharge cycles of test battery The performances such as life-span, highest discharge capacity, circulation volume conservation rate, internal resistance, in full electricity state (open-circuit voltage：4.15V, 4.25V) under The security performances such as test heavy impact test, puncture test.Test result shows：Putting under 2C, 10C and 60C charge-discharge mechanism Electric cycle life respectively be 1012 weeks, 431 weeks, 252 weeks (this circulation volume conservation rate is only 45.5%)；1.0Ah battery Highest discharge capacity is 896mAh (2C)；2.5Ah battery highest discharge capacity is 2376mAh (10C)；1.0Ah battery highest is put Capacitance is 764mAh (60C)；5.0Ah battery highest discharge capacity is 4112mAh (60C)；2C multiplying power, the 500th circulation is held Amount conservation rate 89.2%, the 1000th charge and discharge cycles capability retention are 80.3%；10C multiplying power, the 300th time circulation volume is protected Holdup 78.5% (cycle life only has 431 weeks)；Internal resistance is 27.6m Ω；Heavy impact is tested, puncture test all has short circuit, many Detonation (refers to：Table 1, table 2).
The improvement limited to the technology of the present invention and imitation broadly fall into the scope of protection of the invention, and unaccomplished matter of the present invention is public affairs Know technology.
The lithium ion battery charge-discharge performance test result of the negative plate assembling of table 1 present invention
Table 2 negative plate of the present invention assembling capacity of lithium ion battery, internal resistance and Partial security result of the test

Claims (5)

1. a kind of manufacture method of safe lithium ion power battery cathode piece, its step is：
The first step, by negative pole pole active substance:Cathode conductive agent presses 1:0.002~1:0.01 mass ratio, ball milling mixing 0.5～ 3 hours, obtain negative electrode active material mixture A；By cathode additive agent B according to A:The mass ratio of B is respectively：1:0.001～1: 0.005 ratio, 0.5～4 hour mix homogeneously of ball milling, make negative electrode active material mixture C；
Second step, the sodium carboxymethyl cellulose water that the first step obtains negative electrode active material mixture C quality 1～5% are prepared One-tenth mass percent concentration is 0.5～6.0% aqueous solution, 30～45 DEG C of constant temperature, vacuum stirring 0.5～3 hour, points 3～5 times plus Enter to account for the SB of C mass 2～10%, be simultaneously introduced and account for the carboxymethylcellulose sodium solution water yield 1～5% N-methyl pyrrolidinone solvent, 30 DEG C～45 DEG C constant temperature, vacuum stirring 0.5～3 hour, stir into solvent sizing material D；
3rd step, the negative electrode mix C obtaining the first step divide 3～5 times and are added in solvent sizing material D, control negative electrode mix The mass ratio of C amount of solid and water is 650:Between 1000 ~ 1200, vacuum stirring prepares cathode size, suitably increases the water yield, adjusts Section, control slurry viscosity, in 1800～3200cps, vacuum stirring 2～8 hours, obtain negative electrode active material slurry E；
4th step, with 10～20 μm of Copper Foil for collector F, the slurry one side that obtain the 3rd step or two-sided batch (-type) coating On collector, length in reserve is the collector of 15～45cm, through 75～125 DEG C of dryings, controls surface density 10～24.5mg/ cm2, through to roller roll, control compacted density 1.35～1.85g/cm3, 65～200 μm of pole piece thickness；Through bean noodles, cutting, point Welding electrode ear, adhering polar ear adhesive belt.
2. a kind of safe lithium ion power battery cathode piece according to claim 1 manufacture method it is characterised in that：Institute The negative electrode active material stated is graphite/absorbent charcoal composite material.
3. a kind of safe lithium ion power battery cathode piece according to claim 1 manufacture method it is characterised in that：Institute The cathode conductive agent stated is Super-P, i.e. superfine graphite or super white carbon black or acetylene black, and particle diameter is one of graphite of 30nm Or the mixture of the mass ratioes such as two kinds.
4. a kind of safe lithium ion power battery cathode piece according to claim 1 manufacture method it is characterised in that：Institute The cathode additive agent stated be one of Graphene or CNT or two kinds etc. mass ratio mixing.
5. a kind of safe lithium ion electrokinetic cell according to claim 1 manufacture method it is characterised in that：Described water For deionized water or pure water or one of redistilled water or distilled water.
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CN112186262A (en) * 2020-10-09 2021-01-05 西安交通大学 MLCC structure-based all-solid-state lithium ion battery and preparation method thereof
CN112838200A (en) * 2021-02-02 2021-05-25 衡阳市瑞启新能源有限公司 Semiconductor lithium ion storage battery cathode and preparation method thereof
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Application publication date: 20170222