CN109103496A - A kind of long storage life lithium ion battery and preparation method thereof - Google Patents

A kind of long storage life lithium ion battery and preparation method thereof Download PDF

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Publication number
CN109103496A
CN109103496A CN201810972203.5A CN201810972203A CN109103496A CN 109103496 A CN109103496 A CN 109103496A CN 201810972203 A CN201810972203 A CN 201810972203A CN 109103496 A CN109103496 A CN 109103496A
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negative electrode
lithium ion
storage life
electrode tab
ion battery
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程广玉
高蕾
顾洪汇
王可
解晶莹
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Shanghai Institute of Space Power Sources
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Shanghai Institute of Space Power Sources
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a kind of long storage life lithium ion batteries and preparation method thereof, which includes: shell is arranged in the intracorporal battery core of shell and electrolyte；The battery core includes positive plate, negative electrode tab and the diaphragm for positive plate and negative electrode tab to be isolated；The ratio between reversible capacity and the reversible capacity of positive plate of the negative electrode tab are 0.8:1~2:1；The negative electrode tab is handled through prelithiation, and the prelithiation degree of negative electrode tab is the 10~100% of positive plate reversible capacity.Utilize lithium ion battery prepared by the method for the present invention, by adjusting positive and negative anodes capacity excess ratio, not only vice-minister's storage life lithium ion battery can have been prepared but also two vice-minister's storage life lithium ion batteries can be prepared, the former has long storage life, high-energy density and high-power feature, the latter has long storage life, long circulation life and high-power feature, can satisfy a variety of long storage applications requirements.

Description

A kind of long storage life lithium ion battery and preparation method thereof
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of long storage life lithium ion battery and its preparation Method.
Background technique
In certain fields, battery needs highly charged state storage for a long time as redundant electrical power, possible according to task needs Some months, several years even the more than ten years just using once, it is desirable that power supply makes an immediate response, can with biggish multiplying power continuous discharge, and And has higher specific energy.Traditional zinc-silver reserve battery reserve service life is shorter, needs to activate, specific energy is lower；Thermal cell Has high power discharge ability in short-term, same specific energy is lower, the working time is short and battery temperature is excessively high limits its application； And a lithium primary cell such as lithium thionyl chloride cell cannot achieve big times although having higher specific energy and storage life Rate electric discharge, equally limits its application.
Summary of the invention
It is above-mentioned existing to solve the object of the present invention is to provide a kind of long storage life lithium ion battery and preparation method thereof The problem of technology.
In order to achieve the above objectives, the present invention provides a kind of long storage life lithium ion battery, it includes: shell, setting In the intracorporal battery core of shell and electrolyte；The battery core include positive plate, negative electrode tab and for be isolated positive plate and negative electrode tab every Film；The ratio between reversible capacity and the reversible capacity of positive plate of the negative electrode tab are 0.8:1~2:1；The negative electrode tab is through prelithiation Processing, and the prelithiation degree of negative electrode tab is the 10~100% of positive plate reversible capacity.
Above-mentioned long storage life lithium ion battery, wherein the positive plate includes plus plate current-collecting body and is coated on positive The positive electrode material layer of collection liquid surface；The positive electrode material layer includes positive active material, conductive agent and bonding agent.
Above-mentioned long storage life lithium ion battery, wherein the plus plate current-collecting body is aluminium foil, aluminium foil with holes, aluminium net, nickel Foil, nickel foil with holes or nickel screen；The positive active material is LiCoO2、LiMnO2、LiNi1-x-yCoxMnyO2、LiNi1-x- yCoxAlyO2、LiMn2O4、LiMPO4And Li2MSiO4One of or it is a variety of, wherein 0≤x, y≤1, x+y≤1, M Fe, Co, One of Ni and Mn or a variety of；The conductive agent is super carbon black (SP), carbon nanotube (CNT), gas-phase growth of carbon fibre (VGCF), acetylene black (AB), Ketjen black (ECP) or pitch；The bonding agent is Kynoar (PVDF), butadiene-styrene rubber (SBR) or sodium carboxymethylcellulose (CMC).
Above-mentioned long storage life lithium ion battery, wherein the negative electrode tab include negative current collector and be coated on cathode The negative electrode material layer of collection liquid surface；The negative electrode material layer includes negative electrode active material, conductive agent and bonding agent.
Above-mentioned long storage life lithium ion battery, wherein the negative current collector is copper foil, copper foil with holes, copper mesh, nickel Foil, nickel foil with holes, nickel screen, aluminium foil, aluminium foil with holes or aluminium net；The negative electrode active material is graphite, soft carbon, hard carbon, silicon substrate One of material, tin-based material and lithium titanate are a variety of；The conductive agent is super carbon black, carbon nanotube, vapor phase growth carbon fiber Dimension, acetylene black, Ketjen black or pitch；The bonding agent is Kynoar (PVDF), butadiene-styrene rubber (SBR) or carboxymethyl cellulose Plain sodium (CMC).
Above-mentioned long storage life lithium ion battery, wherein the diaphragm is polypropylene, polyethylene/polypropylene (polypropylene/polypropylene/polypropylene, PP/PE/PP) three-layer membrane, polyethylene (polyethylene, PE) single-layer septum, polypropylene (polypropylene, PP) single-layer septum, surface are aoxidized coated with metal Polyethylene (polyethylene, PE) diaphragm of object, surface be coated with metal oxide polypropylene (polypropylene, PP) diaphragm or surface are coated with polypropylene, polyethylene/polypropylene (polypropylene/ of metal oxide Polypropylene/polypropylene, PP/PE/PP) three-layer membrane.
Above-mentioned long storage life lithium ion battery, wherein the shape of the shell is cylindrical or rectangular.
The present invention also provides a kind of preparation methods of above-mentioned long storage life lithium ion battery, and it includes following steps It is rapid: step 1: production positive plate；Step 2: production negative electrode tab, and control the reversible capacity of negative electrode tab and the reversible capacity of positive plate The ratio between be 0.8:1~2:1；Step 3: the prelithiation degree for carrying out prelithiation to negative electrode tab, and controlling negative electrode tab is that positive plate can The 10~100% of inverse capacity；Step 4: battery core is made in the negative electrode tab after positive plate, diaphragm and prelithiation, then fills battery core Enter in shell and sealed after injecting electrolyte, long storage life lithium ion battery is obtained after chemical conversion and aging.
The preparation method of above-mentioned long storage life lithium ion battery, wherein the method for the prelithiation is that electrochemistry is pre- Lithiumation or physics prelithiation.
The preparation method of above-mentioned long storage life lithium ion battery, wherein the lithium source that the prelithiation uses be dissolved with The solution of lithium or lithium ion, organic electrolyte containing lithium, lithium band or lithium powder.
Compared with the existing technology, the invention has the following advantages:
Realize the long storage life of lithium ion battery key be to solve the problems, such as the self discharge of battery during storage, lithium from Sub- self-discharge of battery includes reversible self discharge and irreversible self discharge, and reversible self discharge is similar to battery regular picture, by dust, Impurity, metal fragment etc. cause inside battery micro-short circuit that a part of lithium ion is caused to return to the phenomenon of anode from cathode, fill again Electric discharge can come back to cathode, and the capacity of loss is reversible, and maximum can reduce reversible self discharge by process modification. And irreversible self discharge is to be caused due to electrode material side reaction itself, structure change, disengaging collector etc., and battery fills When full electricity, active lithium concentrates on cathode, and the side reaction of cathode is the main source for causing battery irreversible capacity loss.And pass through Cathode prelithiation is embedded in a part of lithium ion in cathode in advance, after being assembled into battery, by formation process, anode a part Lithium ion is embedded in cathode or is precipitated in negative terminal surface, and the total active lithium content of cathode is much larger than positive lithium demand, and battery Capacity is determined by anode, therefore, even if after battery is stored for a long time, cathode has certain capacitance loss (active lithium loss), But positive lithium demand is still greater than in the residual activity lithium of cathode, and such battery capacity is virtually free from decaying.Cathode is pre- Lithiumation has actually fundamentally prevented the influence that cathode irreversible capacity loss decays to battery capacity.
For long storage life battery, some application demand does not need charging, that is to say, that battery is One-shot battery, relatively positive excessive than can be lower of such cathode, such as 0.8:1~1.3:1, to realize that higher energy is close Degree, at this point, since capacity of negative plates is not enough to be embedded in all active lithiums, will lead to by the battery of cathode prelithiation after chemical conversion A large amount of lithium metals are precipitated in negative terminal surface, and battery at this time is suitable as once storeing power supply use.And if necessary to long storage Life battery has certain cycle life, and the relatively positive excess of cathode is needed to improve, such as 1.3:1~2:1, can be sacrificed in this way Certain specific energy, but cathode has enough capacity to be embedded in all active lithiums, negative terminal surface do not analyse lithium, thus battery with Common secondary lithium battery is the same, has preferable cycle performance.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the lithium ion battery of one embodiment of the invention；
Fig. 2 is the structural schematic diagram of continuous prelithiation device；
Fig. 3 is that circulating battery comparison diagram is made in embodiment 1, embodiment 2 and comparative example 1.
Specific embodiment
Below in conjunction with attached drawing, by specific embodiment, the invention will be further described, these embodiments are merely to illustrate The present invention is not limiting the scope of the invention.
The present invention provides a kind of long storage life lithium ion battery, it includes: shell 1, the battery core being arranged in shell 1 And electrolyte；The battery core includes positive plate, negative electrode tab and the diaphragm 10 for positive plate and negative electrode tab to be isolated；The negative electrode tab Reversible capacity and the ratio between the reversible capacity of positive plate be 0.8:1~2:1；The negative electrode tab is handled through prelithiation, and negative electrode tab Prelithiation degree be positive plate reversible capacity 10~100%.
The positive plate includes plus plate current-collecting body 8 and the positive electrode material layer 9 coated on 8 surface of plus plate current-collecting body；It is described just Pole material layer 9 includes positive active material, conductive agent and bonding agent.
The plus plate current-collecting body 8 is aluminium foil, aluminium foil with holes, aluminium net, nickel foil, nickel foil with holes or nickel screen；The positive-active Substance is LiCoO2、LiMnO2、LiNi1-x-yCoxMnyO2、LiNi1-x-yCoxAlyO2、LiMn2O4、LiMPO4And Li2MSiO4In It is one or more, wherein one of 0≤x, y≤1, x+y≤1, M Fe, Co, Ni and Mn or a variety of；The conductive agent is super Grade carbon black (SP), carbon nanotube (CNT), gas-phase growth of carbon fibre (VGCF), acetylene black (AB), Ketjen black (ECP) or pitch；Institute Stating bonding agent is Kynoar (PVDF), butadiene-styrene rubber (SBR) or sodium carboxymethylcellulose (CMC).8 thickness of plus plate current-collecting body It is 10~25 μm.
The negative electrode tab includes negative current collector 12 and the negative electrode material layer 11 coated on 12 surface of negative current collector；It is described Negative electrode material layer 11 includes negative electrode active material, conductive agent and bonding agent.
The negative current collector 12 is copper foil, copper foil with holes, copper mesh, nickel foil, nickel foil with holes, nickel screen, aluminium foil, aluminium foil with holes Or aluminium net；The negative electrode active material is one of graphite, soft carbon, hard carbon, silica-base material, tin-based material and lithium titanate or more Kind；The conductive agent is super carbon black, carbon nanotube, gas-phase growth of carbon fibre, acetylene black, Ketjen black or pitch；The bonding Agent is Kynoar (PVDF), butadiene-styrene rubber (SBR) or sodium carboxymethylcellulose (CMC).Negative current collector 12 with a thickness of 6~ 20μm。
The diaphragm 10 is polypropylene, polyethylene/polypropylene (polypropylene/polypropylene/ Polypropylene, PP/PE/PP) three-layer membrane 10, polyethylene (polyethylene, PE) single-layer septum 10, polypropylene (polypropylene, PP) single-layer septum 10, surface be coated with metal oxide polyethylene (polyethylene, PE) every Film 10, surface are coated with polypropylene (polypropylene, PP) diaphragm 10 of metal oxide or surface is aoxidized coated with metal Polypropylene, polyethylene/polypropylene (polypropylene/polypropylene/polypropylene, PP/PE/PP) of object Three-layer membrane 10.
The shell 1 is metal-back all-sealed structure, including but not limited to cylindrical or square structure.
The present invention also provides a kind of preparation methods of above-mentioned long storage life lithium ion battery, and it includes following steps It is rapid:
Step 1: production positive plate；
By positive electrode active materials and PVDF binder and conductive agent in N-Methyl pyrrolidone (N-Methyl Pyrrolidone, NMP) it stirs evenly in solvent, anode sizing agent is made, and anode sizing agent is coated uniformly on plus plate current-collecting body 8 On, positive surface density (two-sided) 16mg/cm2~32mg/cm2, positive master slice is obtained, cuts positive master slice roll-in to obtain anode Piece；
Step 2: production negative electrode tab, and controlling the ratio between the reversible capacity of negative electrode tab and the reversible capacity of positive plate is 0.8:1 ~2:1；
Negative electrode active material and PVDF binder and conductive agent are stirred evenly in nmp solvent be made negative electrode slurry (or Negative electrode active material and CMC, SBR binder and conductive agent are stirred evenly negative electrode slurry is made in deionized water by person), and will Negative electrode slurry is coated uniformly on negative current collector 12, cathode surface density according to the reversible capacity of positive surface density and cathode with The ratio between reversible capacity of anode determines, obtains cathode master slice, cuts cathode master slice roll-in to obtain negative electrode tab；
Step 3: the prelithiation degree for carrying out prelithiation to negative electrode tab, and controlling negative electrode tab is the 10 of positive plate reversible capacity ~100%；The method of the prelithiation is electrochemistry prelithiation or physics prelithiation.The lithium source that the prelithiation uses be dissolved with The solution of lithium or lithium ion, organic electrolyte containing lithium, lithium band or lithium powder.
The extensive prelithiation of cathode carries out before cutting after master slice roll-in, and a small amount of cathode prelithiation is after master slice roll-in is cut It carries out.For electrochemistry prelithiation, pre- lithium is determined by the voltage of negative electrode tab opposing metallic lithium or by the embedding lithium capacity of cathode Change degree；For physics prelithiation, prelithiation is determined by calculation and controls prelithiation degree with lithium band or lithium powder dosage；
Step 4: battery core is made in the negative electrode tab after positive plate, diaphragm 10 and prelithiation, then battery core is fitted into shell 1 And sealed after injecting electrolyte, chemical conversion aging is carried out after shelving 12~48h to get lithium ion battery.Being melted into aging process is 0.05~0.2C electric current charges to 4.0V~4.2V, and 24~120h of aging in 40~55 DEG C of environment.
Embodiment 1
The present embodiment provides a kind of lithium ion batteries, including shell 1, the battery core being arranged in shell 1 and electrolyte, battery core Including positive plate, negative electrode tab and the diaphragm 10 that positive/negative plate is isolated, it is prepared using following methods:
(1) positive plate: being the NCA (LiNi of 185mAh/g with gram volume0.8Co0.15Al0.05O2) it is positive electrode active materials, with Binder PVDF and conductive agent Super-P are mixed evenly in NMP by the mass ratio of 95:2:3, and anode sizing agent is made, presses 26mg/cm2Density by anode sizing agent dual coating with a thickness of 16 μm of width be 300mm aluminium foil on, the anode sizing agent The intermittent application on aluminium foil, the length of dual coating is 855mm, and position is completely coincident, coating gap 8mm, roll-in Afterwards, cutting into width through pole piece cutting machine is 57mm, with a thickness of 90 μm of positive plates；
(2) negative electrode tab: using gram volume for 350mAh/g graphite as positive electrode active materials, with binder PVDF by 97:3 Mass ratio is mixed evenly in NMP, and negative electrode slurry is made, by 14.5mg/cm2Density negative electrode slurry dual coating is existed On the copper foil for being 300mm with a thickness of 10 μm of width, and the ratio between reversible capacity of the reversible capacity of the cathode and anode is 1.08: 1, negative electrode slurry intermittent application on copper foil, the length of dual coating is respectively 919mm and 865mm, and an end position It is completely coincident, coating minimum clearance is 30mm, and after roll-in, cutting into width through pole piece cutting machine is 58.5mm, with a thickness of 107 μm Negative electrode tab；
(3) negative electrode tab prelithiation: negative electrode tab is subjected to prelithiation using continuous prelithiation device, prelithiation capacity is anode The 40% of reversible capacity；
(4) diaphragm 10: using three layers of composite diaphragm of polypropylene, polyethylene/polypropylene (PP/PE/PP) with a thickness of 25 μm 10, width 61mm, volume two；
(5) electrolyte: the LiFP6- ethylene carbonate (EC) of 1.2mol/L/dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC) (volume ratio 1:1:1)；
(6) production of lithium ion battery: positive plate obtained above, diaphragm 10 and negative electrode tab is welded using winding Machine, which is wound and welds positive and negative tab, obtains lithium ion battery cell, is then fitted into battery core in 18650 battery cases 1 simultaneously It is sealed after injection electrolyte, static 48h after fluid injection sealing；
(7) chemical conversion and aging of lithium ion battery: use the electric current of 0.11A (0.05C) by lithium-ion electric made from step (6) Pond charges to 4.1V, and after aging 48h, 1 model of the embodiment of the present invention then is made in 45 DEG C of ovens in lithium ion battery The lithium ion battery of YC18650.
Referring to Fig. 1, prepared lithium ion battery be can specifically include: shell 1, battery cap 2, sealing insulator 3, just Pole 4, liquid injection hole 5, positive pole ear 6, negative lug 7, plus plate current-collecting body 8, positive electrode material layer 9, diaphragm 10, negative electrode material layer 11 With negative current collector 12.
Fig. 2 is continuous prelithiation schematic diagram of device, is only the principle and process that illustrate the continuous prelithiation of cathode, not equivalent In real equipment.The continuous prelithiation device includes cathode let off roll 13, insulation deflector roll 14, lithium metal plate 15, cathode band 16, pre- Lithiumation chamber 17, cleaning chamber 18, drying chamber 19 and prelithiation cathode wind-up roll 20.
Wherein insulation deflector roll 14 is the etching insulative of resistance to organic electrolyte material, preferably polytetrafluoroethylene (PTFE), polypropylene (PP), the materials such as polyethylene (PE), polyvinyl chloride (PVC), polyimides (PI).
Wherein 15 width of lithium metal plate will be wider than cathode width, as close as possible at a distance from cathode, but not with cathode contact.
Organic electrolyte is injected in prelithiation chamber 17, liquid level of electrolyte needs not cross lithium metal plate 15, electrolyte: by hexafluoro Lithium phosphate (LiPF6) is added in solvent, is uniformly mixed and is obtained electrolyte, wherein the solvent is ethylene carbonate (EC), carbon Sour methyl ethyl ester (EMC), dimethyl carbonate (DMC), ethylene carbonate (EC), methyl ethyl carbonate (EMC), carbonic acid two in the solvent The volume ratio EC:EMC:DMC=1:1:1 of methyl esters (DMC), the concentration of lithium hexafluoro phosphate (LiPF6) is 2mol/ in gained electrolyte L。
Cleaning chamber 18 injects organic cleaning agent, and liquid level needs not cross cathode, the preferred DMC of cleaning agent.
Preferably 45~85 DEG C of 19 temperature of drying chamber.
Prelithiation process:
During prelithiation, it is anode, lithium metal plate 15 for cathode with cathode roller, is carried out using charge and discharge instrument or resistance Electric discharge controls cathode prelithiation degree by adjusting discharge current and tape running speed.
Cleaning chamber 18 can be entered after prelithiation, wash off the electrolyte of negative terminal surface.
The cathode that cleaning finishes enters drying chamber 19 and is dried, and enters winding later and completes entire prelithiation process.
Embodiment 2
The present embodiment provides a kind of lithium ion batteries, including shell 1, the battery core being arranged in shell 1 and electrolyte, battery core Including positive plate, negative electrode tab and the diaphragm 10 that positive/negative plate is isolated, it is prepared using following methods:
(1) positive plate: being the NCA (LiNi of 185mAh/g with gram volume0.8Co0.15Al0.05O2) it is positive electrode active materials, with Binder PVDF and conductive agent Super-P are mixed evenly in NMP by the mass ratio of 95:2:3, and anode sizing agent is made, presses 26mg/cm2Density by anode sizing agent dual coating with a thickness of 16 μm of width be 300mm aluminium foil on, the anode sizing agent The intermittent application on aluminium foil, the length of dual coating is 710mm, and position is completely coincident, coating gap 8mm, roll-in Afterwards, cutting into width through pole piece cutting machine is 57mm, with a thickness of 90 μm of positive plates；
(2) negative electrode tab: using gram volume for 350mAh/g graphite as positive electrode active materials, with binder PVDF by 97:3 Mass ratio is mixed evenly in NMP, and negative electrode slurry is made, by 20mg/cm2Density by negative electrode slurry dual coating in thickness Degree is that 10 μm of width are, and the ratio between reversible capacity of the reversible capacity of the cathode and anode is 1.5:1 on the copper foil of 300mm, Negative electrode slurry intermittent application on copper foil, the length of dual coating is respectively 774mm and 720mm, and an end position is complete Full weight is closed, and coating minimum clearance is 30mm, and after roll-in, cutting into width through pole piece cutting machine is 58.5mm, with a thickness of 144 μm Negative electrode tab；
(3) negative electrode tab prelithiation: continuous negative electrode tab is subjected to prelithiation using continuous prelithiation device, prelithiation capacity is The 40% of positive reversible capacity；
(4) diaphragm 10: using three layers of composite diaphragm of polypropylene, polyethylene/polypropylene (PP/PE/PP) with a thickness of 25 μm 10, width 61mm, volume two；
(5) electrolyte: the LiFP6-EC/DMC/EMC (volume ratio 1:1:1) of 1.2mol/L；
(6) production of lithium ion battery: positive plate obtained above, diaphragm 10 and negative electrode tab is welded using winding Machine, which is wound and welds positive and negative tab, obtains lithium ion battery cell, is then fitted into battery core in 18650 battery cases 1 simultaneously It is sealed after injection electrolyte, static 48h after fluid injection sealing,
(7) chemical conversion and aging of lithium ion battery: use the electric current of 0.1A (0.05C) by lithium-ion electric made from step (6) Pond charges to 4.1V, and after aging 48h, 2 model of the embodiment of the present invention then is made in 45 DEG C of ovens in lithium ion battery The lithium ion battery of EC18650.
Comparative example 1
A kind of comparative example of lithium ion battery of the present invention, lithium ion battery described in this comparative example prepared using following methods and At:
(1) positive plate: being the NCA (LiNi of 185mAh/g with gram volume0.8Co0.15Al0.05O2) it is positive electrode active materials, with Binder PVDF and conductive agent Super-P are mixed evenly in NMP by the mass ratio of 95:2:3, and anode sizing agent is made, presses 26mg/cm2Density by anode sizing agent dual coating with a thickness of 16 μm of width be 300mm aluminium foil on, the anode sizing agent The intermittent application on aluminium foil, the length of dual coating is 865mm, and position is completely coincident, coating gap 8mm, roll-in Afterwards, cutting into width through pole piece cutting machine is 57mm, with a thickness of 90 μm of positive plates；
(2) negative electrode tab: using gram volume for 350mAh/g graphite as positive electrode active materials, with binder PVDF by 97:3 Mass ratio is mixed evenly in NMP, and negative electrode slurry is made, by 14.5mg/cm2Density negative electrode slurry dual coating is existed On the copper foil for being 300mm with a thickness of 10 μm of width, and the ratio between reversible capacity of the reversible capacity of the cathode and anode is 1.08: 1, negative electrode slurry intermittent application on copper foil, the length of dual coating is respectively 929mm and 875mm, and an end position It is completely coincident, coating minimum clearance is 30mm, and after roll-in, cutting into width through pole piece cutting machine is 58.5mm, with a thickness of 107 μm Negative electrode tab；
(3) diaphragm 10: using three layers of composite diaphragm of polypropylene, polyethylene/polypropylene (PP/PE/PP) with a thickness of 25 μm 10, width 61mm, volume two；
(4) electrolyte: the LiFP6-EC/DMC/EMC (volume ratio 1:1:1) of 1.2mol/L；
(5) production of lithium ion battery: positive plate obtained above, diaphragm 10 and negative electrode tab are wound using cylindrical battery It is welding integrated be wound and weld positive and negative tab obtain lithium ion battery cell, then by battery core be packed into 18650 battery cases It is sealed in body 1 and after injecting electrolyte, static 48h after fluid injection sealing；
(6) chemical conversion and aging of lithium ion battery: use the electric current of 0.11A (0.05C) by lithium-ion electric made from step (5) Pond charges to 4.1V, and after aging 48h, 1 model of comparative example of the present invention then is made in 45 DEG C of ovens in lithium ion battery The lithium ion battery of DB18650.
The lithium ion battery that above-described embodiment 1-2 and comparative example 1 are prepared is subjected to 0.4A and 20A electric discharge respectively, Blanking voltage 2.5V, discharge capacity, platform voltage are as shown in table 1:
Battery discharge comparison is made in 1. embodiment 1 of table, embodiment 2 and comparative example 1
Group Number 0.4A capacity 20A capacity 20A capacity retention ratio
Embodiment 1 YC18650 2135mAh 2024mAh 94.8%
Embodiment 2 EC18650 1816mAh 1712mAh 94.3%
Comparative example 1 DB18650 2133mAh 2019mAh 94.7%
The lithium ion battery that above-described embodiment 1, embodiment 2 and comparative example 1 are prepared is carried out 0.4A circulation respectively to put Electricity, as a result as shown in Table 2 and Fig. 3:
Circulating battery comparison is made in 2. embodiment 1 of table, embodiment 2 and comparative example 1
Group Number Initial capacity Cycle-index Residual capacity Capacity retention ratio
Embodiment 1 YC18650 2133.0 10 7 0%
Embodiment 2 EC18650 1820.0 100 1865.5 102.5%
Comparative example 1 DB18650 2137.0 100 2208.9 103.4%
Circulation system:
(1) 0.4A constant-current charge turns constant-voltage charge to electric current≤0.1A to 4.1V；
(2) static 10min；
(3) 0.4A constant-current discharge is to 2.5V；
(4) static 10min；
(5) 1-4 step is recycled, until discharge capacity is less than initial capacity 80%, electric discharge terminates.
The lithium ion battery that above-described embodiment 1, embodiment 2 and comparative example 1 are prepared is subjected to storage test respectively, is tied Fruit is as shown in table 3:
Battery storage test is made in 3. embodiment 1 of table, embodiment 2 and comparative example 1
Group Number Initial capacity Keep capacity Conservation rate It is expected that storage life
Embodiment 1 YC18650 2135mAh 2099mAh 98.31% 8-10
Embodiment 2 EC18650 1815mAh 1788mAh 98.51% 8-10
Comparative example 1 DB18650 2130mAh 2006mAh 94.18% 2-3
Storage system:
(1) lithium ion battery that embodiment 1, embodiment 2 and comparative example 1 are prepared respectively takes 1 progress before storage 0.4A is discharged to 2.5V, obtains discharge capacity, the lithium ion battery being prepared as embodiment 1, embodiment 2 and comparative example 1 Initial capacity Q1；
(2) the new battery after in addition respectively taking 1 chemical conversion aging, is held on the environment of 20 ± 5 DEG C of humidity 20%-80% of temperature In carry out 0.4A respectively after 6 months, 6 months and be discharged to 2.5V, be maintained capacity Q2；
(3) 6 months battery capacity conservation rates of storage are obtained with Q2/Q1*100%.
It is compared it can be seen from above-mentioned table 1, table 2,3 data of table and Fig. 3 with the lithium ion battery of comparative example 1, the present invention is real It applies 2 kinds of lithium ion batteries made from example 1 and embodiment 2 and is provided with better shelf characteric, capacity is kept after storage at normal temperature 6 months Rate is still above 98%, it is contemplated that storage life is up to 8-10, and comparative example 1 is kept using the lithium ion battery of traditional handicraft development Rate is only 94%, it is contemplated that storage life is only 2-3.Exactly the process of cathode prelithiation is born during compensating for battery storage The active lithium losing issue of pole, and the loss of negative electrode active lithium is considered as that lithium ion battery poor storage performance, self discharge are biggish Major reason, as long as guaranteeing that the amount of negative electrode active lithium is greater than anode to the demand of lithium, the capacity of battery in practice dependent on Anode, and in common anode material for lithium-ion batteries, the self stability of NCA positive electrode is preferable, and self-discharge characteristics is optimal. In addition the lithium ion battery prepared by the present invention, shows higher power characteristic, has 20A (10C) discharge capability.
It is noted that cycle performance of lithium ion battery made from embodiment 1 is poor, it is the battery because cathode is excessively relatively low Negative terminal surface largely analyses lithium after fully charged, and cyclic process, which easily forms Li dendrite, leads to battery internal short-circuit, therefore this is designed as one Vice-minister's storage life lithium ion battery has high specific energy same as traditional lithium-ion battery, is suitble to not require charging, needs The field application stored for a long time.Cycle performance of lithium ion battery made from embodiment 2 is suitable with traditional lithium-ion battery, be because Cathode is excessively relatively high, although capacity of negative plates is large enough to hold all lithium ions by cathode prelithiation, cathode does not analyse lithium, Therefore this is designed as two vice-minister's storage life lithium ion batteries, sacrifices compared to vice-minister's storage life lithium ion battery certain Energy density, but more excellent cycle performance is shown, it is suitble to the field application for needing battery recycling, storing for a long time.
Realize the long storage life of lithium ion battery key be to solve the problems, such as the self discharge of battery during storage, lithium from Sub- self-discharge of battery includes reversible self discharge and irreversible self discharge, and reversible self discharge is similar to battery regular picture, by dust, Impurity, metal fragment etc. cause inside battery micro-short circuit that a part of lithium ion is caused to return to the phenomenon of anode from cathode, fill again Electric discharge can come back to cathode, and the capacity of loss is reversible, and maximum can reduce reversible self discharge by process modification. And irreversible self discharge is to be caused due to electrode material side reaction itself, structure change, disengaging collector etc., and battery fills When full electricity, active lithium concentrates on cathode, and the side reaction of cathode is the main source for causing battery irreversible capacity loss.And pass through Cathode prelithiation is embedded in a part of lithium ion in cathode in advance, after being assembled into battery, by formation process, anode a part Lithium ion is embedded in cathode or is precipitated in negative terminal surface, and the total active lithium content of cathode is much larger than positive lithium demand, and battery Capacity is determined by anode, therefore, even if after battery is stored for a long time, cathode has certain capacitance loss (active lithium loss), But positive lithium demand is still greater than in the residual activity lithium of cathode, and such battery capacity is virtually free from decaying.Cathode is pre- Lithiumation has actually fundamentally prevented the influence that cathode irreversible capacity loss decays to battery capacity.
For long storage life battery, some application demand does not need charging, that is to say, that battery is One-shot battery, relatively positive excessive than can be lower of such cathode, such as 0.8:1~1.3:1, to realize that higher energy is close Degree, at this point, since capacity of negative plates is not enough to be embedded in all active lithiums, will lead to by the battery of cathode prelithiation after chemical conversion A large amount of lithium metals are precipitated in negative terminal surface, and battery at this time is suitable as once storeing power supply use.And if necessary to long storage Life battery has certain cycle life, and the relatively positive excess of cathode is needed to improve, such as 1.3:1~2:1, can be sacrificed in this way Certain specific energy, but cathode has enough capacity to be embedded in all active lithiums, negative terminal surface do not analyse lithium, thus battery with Common secondary lithium battery is the same, has preferable cycle performance.
In conclusion using lithium ion battery prepared by the method for the present invention, by adjusting positive and negative anodes capacity excess ratio, both Vice-minister's storage life lithium ion battery can be prepared can prepare two vice-minister's storage life lithium ion batteries again, the former has length Storage life, high-energy density and high-power feature, the latter have long storage life, long circulation life and high-power spy Point can satisfy a variety of long storage applications requirements.
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it should be appreciated that above-mentioned Description is not considered as limitation of the present invention.After those skilled in the art have read above content, for of the invention A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.

Claims (10)

1. a kind of long storage life lithium ion battery, which is characterized in that it includes: shell is arranged in the intracorporal battery core of shell and electricity Solve liquid；The battery core includes positive plate, negative electrode tab and the diaphragm for positive plate and negative electrode tab to be isolated；The negative electrode tab it is reversible The ratio between reversible capacity of capacity and positive plate is 0.8:1~2:1；The negative electrode tab is handled through prelithiation, and the pre- lithium of negative electrode tab Change degree is the 10~100% of positive plate reversible capacity.
2. long storage life lithium ion battery as described in claim 1, which is characterized in that the positive plate includes anode collection Body and positive electrode material layer coated on plus plate current-collecting body surface；The positive electrode material layer include positive active material, conductive agent and Bonding agent.
3. long storage life lithium ion battery as claimed in claim 2, which is characterized in that the plus plate current-collecting body be aluminium foil, Aluminium foil, aluminium net, nickel foil, nickel foil with holes or nickel screen with holes；The positive active material is LiCoO2、LiMnO2、LiNi1-x- yCoxMnyO2、LiNi1-x-yCoxAlyO2、LiMn2O4、LiMPO4And Li2MSiO4One of or it is a variety of, wherein 0≤x, y≤1, x One of+y≤1, M Fe, Co, Ni and Mn or a variety of；The conductive agent is super carbon black, carbon nanotube, vapor grown carbon Fiber, acetylene black, Ketjen black or pitch；The bonding agent is Kynoar, butadiene-styrene rubber or sodium carboxymethylcellulose.
4. long storage life lithium ion battery as described in claim 1, which is characterized in that the negative electrode tab includes negative pole currect collecting Body and negative electrode material layer coated on negative current collector surface；The negative electrode material layer include negative electrode active material, conductive agent and Bonding agent.
5. long storage life lithium ion battery as described in claim 1, which is characterized in that the negative current collector be copper foil, Copper foil, copper mesh, nickel foil, nickel foil with holes, nickel screen, aluminium foil, aluminium foil with holes or aluminium net with holes；The negative electrode active material be graphite, One of soft carbon, hard carbon, silica-base material, tin-based material and lithium titanate are a variety of；The conductive agent is super carbon black, carbon nanometer Pipe, gas-phase growth of carbon fibre, acetylene black, Ketjen black or pitch；The bonding agent is Kynoar, butadiene-styrene rubber or carboxymethyl Sodium cellulosate.
6. long storage life lithium ion battery as described in claim 1, which is characterized in that the diaphragm is polypropylene/poly- second The polyethylene of alkene/polypropylene three-layer membrane, polyethylene single-layer septum, polypropylene single-layer septum, surface coated with metal oxide The polypropylene, polyethylene of polypropylene diaphragm or surface coated with metal oxide of diaphragm, surface coated with metal oxide/poly- Propylene three-layer membrane.
7. long storage life lithium ion battery as described in claim 1, which is characterized in that the shape of the shell is cylinder Or it is rectangular.
8. a kind of preparation method of the long storage life lithium ion battery as described in claim 1-7 any one, feature exist In it includes following steps: step 1: production positive plate；Step 2: production negative electrode tab, and control the reversible capacity of negative electrode tab with The ratio between reversible capacity of positive plate is 0.8:1~2:1；Step 3: prelithiation being carried out to negative electrode tab, and controls the pre- lithium of negative electrode tab Change degree is the 10~100% of positive plate reversible capacity；Step 4: electricity is made in the negative electrode tab after positive plate, diaphragm and prelithiation Then battery core is fitted into shell and seals after injecting electrolyte, long storage life lithium ion is obtained after chemical conversion and aging by core Battery.
9. the preparation method of long storage life lithium ion battery as claimed in claim 8, which is characterized in that the prelithiation Method is electrochemistry prelithiation or physics prelithiation.
10. the preparation method of long storage life lithium ion battery as claimed in claim 8, which is characterized in that the prelithiation The lithium source used is dissolved with the solution of lithium or lithium ion, organic electrolyte containing lithium, lithium band or lithium powder.
CN201810972203.5A 2018-08-24 2018-08-24 A kind of long storage life lithium ion battery and preparation method thereof Pending CN109103496A (en)

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Application publication date: 20181228