CN103560250A - Lithium ion battery adopting lithium-rich manganese-based material as positive electrode and preparation method of lithium ion battery - Google Patents
Lithium ion battery adopting lithium-rich manganese-based material as positive electrode and preparation method of lithium ion battery Download PDFInfo
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Abstract
The invention discloses a lithium ion battery adopting a lithium-rich manganese-based material as a positive electrode and a preparation method of the lithium ion battery. The lithium ion battery adopting the lithium-rich manganese-based material as the positive electrode comprises a positive electrode, a positive electrode surface coating, a negative electrode, a diaphragm and electrolyte. The lithium ion battery adopting the lithium-rich manganese-based material as the positive electrode has the advantages of high energy density, good multiplying power property and long cycling service life.
Description
Technical field
Invention relates to a kind of lithium ion battery and preparation method thereof, relates in particular to and a kind ofly take lithium-rich manganese-based material as anodal lithium ion battery and preparation method thereof.
Background technology
Lithium-ion-power cell becomes the ideal lift-launch power supply of the energy-conservation accumulator car without environment pollution such as pure electric automobile, plug-in hybrid-power automobile due to its performance advantage.In recent years, the energy density of lithium ion battery and cycle life have been proposed to more and more higher requirement, to meet improving constantly of electric automobile during traveling mileage and useful life.Positive electrode is the key factor that determines performance of lithium ion battery, directly affects energy density, specific power characteristic, temperature characterisitic and the security feature of battery.In current technology, what be widely used and research and develop is with LiFePO4 (LiFePO
4), nickle cobalt lithium manganate (LiNiCoMnO
2) or spinel lithium manganate (LiMn
2o
4) be anodal, the material system that the graphite of take is negative pole.But the shortcoming that also exists some to be difficult at all overcome.Although adopt the circulation of lithium ion battery normal temperature and the fail safe of LiFePO4/graphite system good, cell voltage platform is only 3.2V, has the problems such as energy density is lower, batch consistency is poor.Spinel lithium manganate has that voltage platform is high, the advantage of good rate capability aspect, but the high-temperature digestion of intrinsic John-Teller effect and manganese causes its cycle life, particularly high temperature cyclic performance is poor, is difficult to reach automobile-used life requirements.Adopting the lithium ion battery voltage platform of nickle cobalt lithium manganate/graphite system is 3.6V, and energy density can reach 150-180Wh/kg, but has the problems such as poor safety performance.
In recent years, the lithium-rich manganese-based solid solution cathode material with high power capacity gets more and more people's extensive concerning, and this material is based on stratiform Li
2mnO
3and LiMO
2the solid solution of structure, chemical formula is xLi
2mnO
3(1-x) LiMO
2(M=Mn, Ni, Co).Such material is being greater than under the charging voltage of 4.6V, and specific capacity is higher, and energy density is high.Chinese invention patent 101694876A has announced lithium-rich manganese-based anode material Li[Li (1-2x)/3Nix-a-yMyMn (2-x)/3-b] O
2(M=Co, Al, Ti, Mg, Cu) and preparation method thereof.The discharge capacity of this material 4.6-2.5V voltage window reaches 250mAh/g.Chinese invention patent 103050683A has also announced a kind of preparation method of heterogeneous manganese based solid solution composite positive pole.By at Novel multi-phase manganese based solid solution surface recombination nanometer high conductivity Graphene, prepare heterogeneous manganese based solid solution composite positive pole, this material specific capacity is up to 268mAh/g, and first charge-discharge efficiency reaches 85%, and multiplying power and cryogenic property are obviously promoted.Demonstrate this material potential application foreground aspect high energy density lithium ion power battery anode material.
At present, adopting lithium-rich manganese-based material, be in anodal lithium ion battery technical scheme, mainly by improving charging voltage and adopting high voltage organic electrolyte system to obtain higher energy density and cycle life, as Chinese invention patent CN102544575A has announced a kind of lithium-rich manganese-based power battery and manufacture method thereof, the 0.5C discharge energy density of this battery under 2.0-4.6V condition is 212.35Wh/kg.In Chinese invention patent CN102315481A, announced polynary lithium-ions battery of the rich lithium of a kind of high specific energy and preparation method thereof, this battery adopts fluorine-containing high voltage withstanding organic electrolyte system.But from the angle of practical application, the deficiency of this technical scheme is: when promoting discharge capacity of the cell and energy density by raising battery charging voltage, battery is Efficiency Decreasing first, is only 60-70%; Battery high rate performance is poor, and capacity attenuation is fast, and cycle life is poor, is difficult to practical requirement.
Based on this, the invention provides the lithium ion battery of the lithium-rich manganese-based anode that a kind of employing contains face coat, when improving energy content of battery density, can significantly promote battery high rate performance and cycle life.
Summary of the invention
In view of this, the object of the invention is to overcome in prior art the shortcomings such as lithium ion battery energy density is low, provide a kind of and take lithium-rich manganese-based material as anodal lithium ion battery, when improving lithium-rich manganese-based lithium ion battery energy density, promote battery high rate performance and cycle life.
For this reason, the invention provides and a kind ofly take lithium-rich manganese-based material as anodal lithium ion battery, comprise positive pole, anodal face coat, negative pole, barrier film and electrolyte, described positive pole comprises positive active material 80-95%(weight ratio), conductive agent 3-18%(weight ratio), binding agent 2-17%(weight ratio), described positive active material is lithium-rich manganese-based material or the surface coated lithium-rich manganese-based material of process;
Described anodal face coat comprises nano material 85-97%(weight ratio), binding agent 3-15%(weight ratio), described nano material is one or more the combination in nano-metal-oxide, nano metal nitride, and described binding agent is a kind of in SBR and CMC combination, PVDF, PTFE, PVDF-HFP, polyacrylate;
Described negative pole comprises negative electrode active material 80-95%(weight ratio), conductive agent 3-18%(weight ratio), binding agent 2-17%(weight ratio) and, described negative electrode active material is graphite, hard carbon, soft carbon, silicon, tin, phosphorus, SnO
2, Co
3o
4, Fe
2o
3, Li
4ti
5o
12, a kind of in CuO, silicon-base alloy, kamash alloy, Mg base hydrogen bearing alloy or wherein several;
Described conductive agent is one or more the mixing in superconductive carbon black, electrically conductive graphite, flaky graphite, carbon fiber, carbon nano-tube; Described binding agent is a kind of in SBR and CMC combination, PVDF, PTFE, PVDF-HFP; Described electrolyte comprises lithium salts, organic solvent, film for additive.
Preferably, the general formula of described lithium-rich manganese-based material is xLi
2mnO
3(1-x) LiMO
2(any one in M=Mn, Ni, Co, Cr, Zn, Mg, Al, Ti), 0<x<1.
Preferably, the surperficial clad material of described surface coated lithium-rich manganese-based material is Al
2o
3, MgO, CaO, TiO
2, a kind of in ZnO, ZrO, conducting high polymers thing, carbon, Graphene or wherein several.
Preferably, the one side thickness of described anodal face coat is 1-10 μ m.
Preferably, in described anodal face coat, nano material is one or more the combination in nano aluminium oxide, nano calcium oxide, nano magnesia, nano zircite, nano zine oxide, nano-titanium oxide, nano aluminum nitride, Nano titanium nitride.
Preferably, in described anodal face coat, the average grain diameter D50 of nano material is 100-2000 nm, and specific area is 2-30m
2/ g.
Preferably, the lithium salts in described electrolyte is LiPF
6, LiBF
6, LiClO
4, LiN (CF
3sO
2)
2, Li (CF
3sO
2)
3in a kind of or wherein several; Organic solvent in described electrolyte is two or more the combination in ethylene carbonate (EC), propene carbonate (PC), butylene, dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), fluorinated ethylene carbonate (FEC), glutaronitrile (CLN), adiponitrile (ADN), the first and second sulfones (EMS), methoxy ethyl methyl sulfone (MEMS); Film for additive in described electrolyte is one or both the combination in vinylene carbonate (VC), propylene sulfite (PS).
The invention provides described a kind of preparation method that lithium-rich manganese-based material is anodal lithium ion battery of take, comprise the following steps:
The preparation of anode sizing agent, cathode size comprises the following steps: by positive active material 80-95%(weight ratio), conductive agent 3-18%(weight ratio), binding agent 2-17%(weight ratio) add respectively in organic solvent, after high-speed stirred, be configured to anode sizing agent; By negative electrode active material 80-95%(weight ratio), conductive agent 3-18%(weight ratio), binding agent 2-17%(weight ratio) add respectively in organic solvent or deionized water, after high-speed stirred, be configured to cathode size;
The preparation of anodal face coat slurry comprises the following steps: by nano material 85-97%(weight ratio), binding agent 3-15%(weight ratio), add respectively in organic solvent or deionized water, after high-speed stirred, be configured to face coat slurry;
The preparation of anode pole piece, cathode pole piece comprises the following steps: anode sizing agent is coated in to aluminium foil equably by coating machine two-sided, after baking, roll-in, obtaining one side density is 5-25mg/cm
2, compacted density is 2.3-3.2g/cm
3positive plate, anodal face coat slurry is coated on the positive plate after roll-in equably, after film-making, obtain anode pole piece; Cathode size is coated in to Copper Foil equably by coating machine two-sided, after baking, roll-in, film-making, obtaining one side density is 4-12mg/cm
2, compacted density is 0.6-1.5g/ cm
3cathode pole piece;
The preparation of battery core comprises the following steps: mode that the anode pole piece preparing, cathode pole piece are replaced by positive and negative electrode is stacking or be wound into battery core, and wherein both positive and negative polarity separates with barrier film, and guarantees that Fu Liao district negative pole size is greater than anodal size; Positive and negative electrode lug is by being welded and fixed; Battery core is put into battery container, on battery container, leave electrolyte inlet; Battery core is removed moisture at 60-90 ° of C baking 12-48h;
Encapsulation fluid injection: seal liquid injection port injecting electrolyte in from electrolyte inlet to battery container.
Change into: adopt stepped charging modes to change on packaged battery, the charging voltage upper limit is controlled at 4.35-4.6V, after constant voltage is full of, transfers 4.35-4.6V constant voltage charge to, and charging current is 0.01-0.5C, along with the rising of charging voltage, reduce gradually charging current.
From above technical scheme provided by the invention, the present invention has following technique effect:
(1) lithium ion power battery cathode active material adopts lithium-rich manganese-based material, and this material is by stratiform Li
2mnO
3and LiMO
2the solid solution that structure forms, chemical formula is xLi
2mnO
3(1-x) LiMO
2(any one in M=Mn, Ni, Co, Cr, Zn, Mg, Al, Ti), 0<x<1.When this material is during at electronegative potential, there is 1/2 Li from LiMO
2in component, deviate from.Meanwhile, Li
2mnO
3in charge and discharge process, play a part to stablize anode structure; When this material is during at high potential, LiMO
2remaining Li and Li in component
2mnO
3li can deviate from gradually, there is new electrochemistry platform, thereby make the specific capacity of this material be greater than 250mAh/g, the lithium ion battery of being prepared by this material has advantages of that energy density is high;
(2) be coated in the nano-material coating on lithium-rich manganese-based anode surface and contain hole, improve the porosity of anode pole piece, strengthen the anodal embedding ability to lithium ion, thereby improve efficiency first, discharge capacity and the energy density of battery; Meanwhile, the nano-material coating that is coated in lithium-rich manganese-based anode surface can strengthen the anodal wettability to electrolyte, improves ionic conduction ability, thereby improves battery high rate performance; On the other hand, anodal surface-coated nano-material coating can improve the interface stability between positive electrode and electrolyte, electrolyte decomposition when alleviating battery and being charged to high voltage, thus make battery when thering is higher energy density, have advantages of and have extended cycle life.
(3) be coated in the nano-material coating on lithium-rich manganese-based anode surface, can intercept Li dendrite, burr etc., prevent the internal short-circuit between positive pole and negative pole, improve the security performance of battery.
(4) by adopting little electric current, stepped forming technology, can alleviate the structural change of lithium-rich manganese-based material in charge and discharge process, and battery cycle life is provided.
Accompanying drawing explanation
Fig. 1 be take lithium-rich manganese-based material as anodal pole piece structure schematic diagram in embodiment 1.
Fig. 2 is respectively according to the discharge curve of the lithium ion battery of embodiment 1, embodiment 2, embodiment 3 and comparative example 1 preparation.
Fig. 3 is respectively according to the loop test figure of the lithium ion battery of embodiment 1 and comparative example 1 preparation.
Fig. 4 is according to the multiplying power discharging curve chart of the lithium ion battery of embodiment 1 preparation.
Fig. 5 is according to the multiplying power discharging curve chart of the lithium ion battery of comparative example 1 preparation.
Fig. 6 is respectively according to the charge and discharge cycles resolution chart of the lithium ion battery of embodiment 2 and embodiment 3 preparations.
Fig. 7 is according to the multiplying power discharging curve chart of the lithium ion battery of embodiment 2 preparations.
Fig. 8 is according to the multiplying power discharging curve chart of the lithium ion battery of embodiment 3 preparations.
Wherein, 1-table is coated with slurry 2-anode sizing agent 3-aluminium foil 4-anode sizing agent 5-table and is coated with slurry.
Embodiment
In order to make those skilled in the art person understand better the present invention program, below the present invention is described in further detail:
The invention provides and a kind ofly take lithium-rich manganese-based material as anodal lithium ion battery, comprise positive pole, anodal face coat, negative pole, barrier film and electrolyte, described positive pole comprises positive active material 80-95%(weight ratio), conductive agent 3-18%(weight ratio), binding agent 2-17%(weight ratio), described positive active material is lithium-rich manganese-based material or the surface coated lithium-rich manganese-based material of process, select surface coated lithium-rich manganese-based material can improve battery efficiency, strengthen the structural stability of lithium-rich manganese-based material in discharging and recharging, improve cycle performance;
Described anodal face coat comprises nano material 85-97%(weight ratio), binding agent 3-15%(weight ratio), described nano material is one or more the combination in nano-metal-oxide, nano metal nitride, and described binding agent is a kind of in SBR and CMC combination, PVDF, PTFE, PVDF-HFP, polyacrylate; The slurry of described face coat is coated in the two sides of lithium-rich manganese-based anode, and this coating has good ion ducting capacity and electrolyte wettability, and can strengthen the stability between positive pole and electrolyte interface, improves battery high rate performance and cycle life;
Described negative pole comprises negative electrode active material 80-95%(weight ratio), conductive agent 3-18%(weight ratio), binding agent 2-17%(weight ratio) and, described negative electrode active material is graphite, hard carbon, soft carbon, silicon, tin, phosphorus, SnO
2, Co
3o
4, Fe
2o
3, Li
4ti
5o
12, a kind of in CuO, silicon-base alloy, kamash alloy, Mg base hydrogen bearing alloy or wherein several;
Described conductive agent is one or more the mixing in superconductive carbon black, electrically conductive graphite, flaky graphite, carbon fiber, carbon nano-tube; Described binding agent is a kind of in SBR and CMC combination, PVDF, PTFE, PVDF-HFP; Described electrolyte comprises lithium salts, organic solvent, film for additive, is high pressure resistant organic electrolyte.
The general formula of described lithium-rich manganese-based material is xLi
2mnO
3(1-x) LiMO
2(any one in M=Mn, Ni, Co, Cr, Zn, Mg, Al, Ti), 0<x<1.
The surperficial clad material of described surface coated lithium-rich manganese-based material is Al
2o
3, MgO, CaO, TiO
2, a kind of in ZnO, ZrO, conducting high polymers thing, carbon, Graphene or wherein several.
The one side thickness of described anodal face coat is 1-10 μ m.
In described anodal face coat, nano material is one or more the combination in nano aluminium oxide, nano calcium oxide, nano magnesia, nano zircite, nano zine oxide, nano-titanium oxide, nano aluminum nitride, Nano titanium nitride.
In described anodal face coat, the average grain diameter D50 of nano material is 100-2000 nm, and specific area is 2-30m
2/ g.
Lithium salts in described electrolyte is LiPF
6, LiBF
6, LiClO
4, LiN (CF
3sO
2)
2, Li (CF
3sO
2)
3in a kind of or wherein several; Organic solvent in described electrolyte is two or more the combination in ethylene carbonate (EC), propene carbonate (PC), butylene, dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), fluorinated ethylene carbonate (FEC), glutaronitrile (CLN), adiponitrile (ADN), the first and second sulfones (EMS), methoxy ethyl methyl sulfone (MEMS); Film for additive in described electrolyte is one or both the combination in vinylene carbonate (VC), propylene sulfite (PS).Described electrolyte has high voltage withstanding characteristic, can guarantee that battery discharges and recharges more than 4.6V.
The invention provides described a kind of preparation method that lithium-rich manganese-based material is anodal lithium ion battery of take, comprise the following steps:
The preparation of anode sizing agent, cathode size comprises the following steps: by positive active material 80-95%(weight ratio), conductive agent 3-18%(weight ratio), binding agent 2-17%(weight ratio) add respectively in organic solvent, after high-speed stirred, be configured to anode sizing agent; By negative electrode active material 80-95%(weight ratio), conductive agent 3-18%(weight ratio), binding agent 2-17%(weight ratio) add respectively in organic solvent or deionized water, after high-speed stirred, be configured to cathode size;
The preparation of anodal face coat slurry comprises the following steps: by nano material 85-97%(weight ratio), binding agent 3-15%(weight ratio), add respectively in organic solvent or deionized water, after high-speed stirred, be configured to face coat slurry;
The preparation of anode pole piece, cathode pole piece comprises the following steps: anode sizing agent is coated in to aluminium foil equably by coating machine two-sided, after baking, roll-in, obtaining one side density is 5-25mg/cm
2, compacted density is 2.3-3.2g/cm
3positive plate, anodal face coat slurry is coated on the positive plate after roll-in equably, after film-making, obtain anode pole piece; Cathode size is coated in to Copper Foil equably by coating machine two-sided, after baking, roll-in, film-making, obtaining one side density is 4-12mg/cm
2, compacted density is 0.6-1.5g/ cm
3cathode pole piece;
The preparation of battery core comprises the following steps: mode that the anode pole piece preparing, cathode pole piece are replaced by positive and negative electrode is stacking or be wound into battery core, and wherein both positive and negative polarity separates with barrier film, and guarantees that Fu Liao district negative pole size is greater than anodal size; Positive and negative electrode lug is by being welded and fixed; Battery core is put into battery container, on battery container, leave electrolyte inlet; Battery core is removed moisture at 60-90 ° of C baking 12-48h;
Encapsulation fluid injection: seal liquid injection port injecting electrolyte in from electrolyte inlet to battery container;
Change into: adopt stepped charging modes to change on packaged battery, the charging voltage upper limit is controlled at 4.35-4.6V, after constant voltage is full of, transfers 4.35-4.6V constant voltage charge to, and charging current is 0.01-0.5C, along with the rising of charging voltage, reduce gradually charging current.
To the present invention be described in more detail by embodiment below:
(1) lithium-rich manganese-based material, 4%(weight ratio anodal, the cathode size of preparation: by 93%(weight ratio)) conductive black, 3%(weight ratio) PVDF join respectively in NMP, after high-speed stirred, be uniformly mixed into anode sizing agent; By 93%(weight ratio) Delanium, 3%(weight ratio) conductive black, 1.5%(weight ratio) CMC and 2.5%(weight ratio) SBR join respectively in deionized water, after high-speed stirred, be uniformly mixed into cathode size.
(2) prepare anode pole piece, cathode pole piece: with reference to figure 1, the anode sizing agent preparing 2, anode sizing agent 4 are evenly coated in to the two sides of aluminium foil 3 by coating machine, one side surface density is 18.5 mg/cm
2, drying, after roll-in, obtains anode pole piece.The table painting slurry 1, the table that contain 90% (weight ratio) nano aluminium oxide and 10% (weight ratio) binding agent are coated with to slurry 5 and are evenly coated on the anode pole piece after roll-in, coating layer thickness is about 6 μ m, prepares after drying the lithium-rich manganese-based anode that contains face coat;
Prepare cathode pole piece: the cathode size preparing is evenly coated in to the two sides of Copper Foil by coating machine, one side surface density is 11.5 mg/cm
2, drying, after roll-in, obtains cathode pole piece.
(3) prepare battery core: mode that the positive and negative electrode pole piece preparing is replaced by positive and negative electrode is stacking or be wound into battery core, and wherein both positive and negative polarity separates with barrier film, and guarantees that Fu Liao district negative pole size is greater than anodal size; Positive and negative electrode lug is by being welded and fixed; Battery core is put into battery container, on battery container, leave electrolyte inlet; Battery core is removed moisture at 80 ° of C baking 24h.
(4) encapsulation fluid injection: seal liquid injection port injecting the high pressure resistant electrolyte of 100g in from electrolyte inlet to battery container.
(5) change into: adopt stepped charging modes to change on packaged battery, first battery is arrived to 4.2V with 0.05C-0.2C current charges, and the gas of eliminating generation, continuation with 0.02-0.05C current charges to 4.35V, then with 0.01-0.02C electric current constant current charge to 4.6V, transfer 4.6V constant voltage charge to, again the gas producing in battery charging process is discharged, and seal exhaust passage.After 4.6-3.0V voltage range carries out discharging and recharging for twice again, prepare the lithium ion battery of embodiment 1.
The discharge curve of battery as shown in Figure 2, from curve, can find out that battery 0.5C discharge capacity under 4.6-3.0V condition is 25800mAh, its average working voltage is 3.70V, and recording battery weight is 428.31g, and the energy density that calculates this battery is 222.88Wh/kg.
Comparative example 1
(1) preparation positive pole, cathode size: the PVDF of the conductive black, 3% (weight ratio) of the lithium-rich manganese-based material, 4% (weight ratio) of 93% (weight ratio) is joined respectively in NMP, after high-speed stirred, be uniformly mixed into anode sizing agent; The SBR of the CMC and 2.5% (weight ratio) of the conductive black of the Delanium of 93% (weight ratio), 3% (weight ratio), 1.5% (weight ratio) is joined respectively in deionized water, after high-speed stirred, be uniformly mixed into cathode size.
(2) prepare positive and negative electrode pole piece: the anode sizing agent preparing is evenly coated in to the two sides of aluminium foil by coating machine, one side surface density is 18.5 mg/cm
2, drying, after roll-in, obtains anode pole piece.This anode pole piece surface is not containing face coat.The cathode size preparing is evenly coated in to the two sides of Copper Foil by coating machine, one side surface density is 9 mg/cm
2, drying, after roll-in, obtains cathode pole piece.
(3) prepare battery core: mode that the positive and negative electrode pole piece preparing is replaced by positive and negative electrode is stacking or be wound into battery core, and wherein both positive and negative polarity separates with barrier film, and guarantees that Fu Liao district negative pole size is greater than anodal size; Positive and negative electrode lug is by being welded and fixed; Battery core is put into battery container, on battery container, leave electrolyte inlet; Battery core is removed moisture at 80 ° of C baking 24h.
(4) encapsulation fluid injection: seal liquid injection port injecting the high pressure resistant electrolyte of 100g in from electrolyte inlet to battery container.
(5) change into: adopt stepped charging modes to change on packaged battery, first battery is arrived to 4.2V with 0.05C-0.2C current charges, and the gas of eliminating generation, continuation with 0.02-0.05C current charges to 4.35V, then with 0.01-0.02C electric current constant current charge to 4.6V, transfer 4.6V constant voltage charge to, again the gas producing in battery charging process is discharged, and seal exhaust passage.After 4.6-3.0V voltage range carries out discharging and recharging for twice again, prepare comparative example 1 lithium ion battery.
The discharge curve of battery as shown in Figure 2, from curve, can find out that comparative example 1 battery 0.5C discharge capacity under 4.6-3.0V condition is 25153mAh, its average working voltage is 3.67V, and recording battery weight is 420.40g, and the energy density that calculates this battery is 219.58Wh/kg.
As shown in Figure 3, comparative example 1 lithium ion battery obtaining is done to cycle life test, circulation is made as 0.5C charging/0.5C electric discharge.As can be seen from the figure, after the lithium ion battery circulation 150 times of the uncoated face coat in anode pole piece surface, battery capacity declines rapidly, capability retention is 74.7%, show that the lithium-rich manganese-based anode structural change under high voltage that does not contain face coat is remarkable, anodal unstable with electrolyte interface, and the lithium-rich manganese-based anode that adopts surface-coated can strengthen stability anodal and electrolyte interface, improve battery cycle life.
Comparative example 1 battery obtaining is done to multiplying power discharging test, and discharge-rate is made as 0.5C, 1C, 3C, 5C.As shown in Figure 5, under normal temperature environment, battery is respectively 70.2% and 59.7% at the capability retention of 3C and 5C, shows that the lithium-rich manganese-based anode structural change under high voltage that does not contain face coat is remarkable, polarizes larger, and high rate performance is poor.
(1) preparation positive pole, cathode size: the PVDF of the conductive black, 2% (weight ratio) of the lithium-rich manganese-based material, 3% (weight ratio) of 95% (weight ratio) is joined respectively in NMP, after high-speed stirred, be uniformly mixed into anode sizing agent; The SBR of the CMC and 1.5% (weight ratio) of the conductive black of the Delanium of 95% (weight ratio), 3% (weight ratio), 0.5% (weight ratio) is joined respectively in deionized water, after high-speed stirred, be uniformly mixed into cathode size.
(2) prepare anode pole piece, cathode pole piece: the anode sizing agent preparing is evenly coated in to the two sides of aluminium foil by coating machine, one side surface density is 18.5 mg/cm
2, drying, after roll-in, obtains anode pole piece.The slurry that contains 97% (weight ratio) nano aluminium oxide and 3% (weight ratio) binding agent is evenly coated on the anode pole piece after roll-in, prepares after drying the lithium-rich manganese-based anode that contains face coat;
Prepare cathode pole piece: the cathode size preparing is evenly coated in to the two sides of Copper Foil by coating machine, one side surface density is 11.5 mg/cm
2, drying, after roll-in, obtains cathode pole piece.
(3) prepare battery core: mode that the positive and negative electrode pole piece preparing is replaced by positive and negative electrode is stacking or be wound into battery core, and wherein both positive and negative polarity separates with barrier film, and guarantees that Fu Liao district negative pole size is greater than anodal size; Positive and negative electrode lug is by being welded and fixed; Battery core is put into battery container, on battery container, leave electrolyte inlet; Battery core is removed moisture at 80 ° of C baking 24h.
(4) encapsulation fluid injection: seal liquid injection port injecting the high pressure resistant electrolyte of 100g in from electrolyte inlet to battery container.
(5) change into: adopt stepped charging modes to change on packaged battery, first battery is arrived to 4.2V with 0.05C-0.2C current charges, and the gas of eliminating generation, continuation with 0.02-0.05C current charges to 4.35V, then with 0.01-0.02C electric current constant current charge to 4.6V, transfer 4.6V constant voltage charge to, again the gas producing in battery charging process is discharged, and seal exhaust passage.Then with 0.1-0.2C current discharge to 2.5V.Next, in 4.2-2.5V voltage range, with 0.2-0.5C electric current, discharge and recharge twice again, prepare embodiment 2 lithium ion batteries.
The charging and discharging curve of battery as shown in Figure 2, from curve, can find out that embodiment 2 batteries 0.5C discharge capacity under 4.2-2.5V condition is 25918mAh, its average working voltage is 3.64V, and recording battery weight is 481.55g, and the energy density that calculates this battery is 195.91Wh/kg.
(1) lithium-rich manganese-based material, 10%(weight ratio anodal, the cathode size of preparation: by 85%(weight ratio)) conductive black, 5%(weight ratio) PVDF join respectively in NMP, after high-speed stirred, be uniformly mixed into anode sizing agent; By 80%(weight ratio) Delanium, 15%(weight ratio) conductive black, 2%(weight ratio) CMC and 3%(weight ratio) SBR join respectively in deionized water, after high-speed stirred, be uniformly mixed into cathode size.
(2) prepare anode pole piece, cathode pole piece: the anode sizing agent preparing is evenly coated in to the two sides of aluminium foil by coating machine, one side surface density is 15 mg/cm
2, drying, after roll-in, obtains anode pole piece.To contain 85%(weight ratio) slurry of nano aluminium oxide and 15% (weight ratio) binding agent is evenly coated on the anode pole piece after roll-in, prepares after drying the lithium-rich manganese-based anode that contains face coat;
Prepare cathode pole piece: the cathode size preparing is evenly coated in to the two sides of Copper Foil by coating machine, one side surface density is 9 mg/cm
2, drying, after roll-in, obtains cathode pole piece.
(3) prepare battery core: mode that the positive and negative electrode pole piece preparing is replaced by positive and negative electrode is stacking or be wound into battery core, and wherein both positive and negative polarity separates with barrier film, and guarantees that Fu Liao district negative pole size is greater than anodal size; Positive and negative electrode lug is by being welded and fixed; Battery core is put into battery container, on battery container, leave electrolyte inlet; Battery core is removed moisture at 80 ° of C baking 24h.
(4) encapsulation fluid injection: seal liquid injection port injecting the high pressure resistant electrolyte of 100g in from electrolyte inlet to battery container.
(5) change into: adopt stepped charging modes to change on packaged battery, first battery is arrived to 4.2V with 0.05C-0.2C current charges, and the gas of eliminating generation, continuation with 0.02-0.05C current charges to 4.35V, transfer 4.35V constant voltage charge to, again the gas producing in battery charging process is discharged, and seal exhaust passage.Then in 4.35-3.0V voltage range, with 0.2-0.5C electric current, discharge and recharge twice again, prepare embodiment 3 lithium ion batteries.
The charging and discharging curve of embodiment 3 batteries as shown in Figure 2, from curve, can find out that battery 0.5C discharge capacity under 4.35-3.0V condition is 25514 mAh, its average working voltage is 3.76V, and recording battery weight is 506.63g, and the energy density that calculates this battery is 189.32Wh/kg.
The lithium-rich manganese-based material of employing provided by the invention is anodal lithium ion battery, have energy density high, have extended cycle life, the advantage of good rate capability, further, by adjusting battery formation voltage, can alleviate the structural change of lithium-rich manganese-based material in charge and discharge process, battery is when obtaining higher energy density, and battery cycle life further promotes.And under the condition of the existing technology of not obvious change, the method according to this invention can easier prepare this lithium ion battery with high energy density, this lithium ion battery can be widely used in the fields such as electric automobile, energy storage, has broad application prospects.
From above technical scheme provided by the invention, the present invention has following technique effect:
(1) lithium ion power battery cathode active material adopts lithium-rich manganese-based material, and this material is by stratiform Li
2mnO
3and LiMO
2the solid solution that structure forms, chemical formula is xLi
2mnO
3(1-x) LiMO
2(any one in M=Mn, Ni, Co, Cr, Zn, Mg, Al, Ti), 0<x<1.When this material is during at electronegative potential, there is 1/2 Li from LiMO
2in component, deviate from.Meanwhile, Li
2mnO
3in charge and discharge process, play a part to stablize anode structure; When this material is during at high potential, LiMO
2remaining Li and Li in component
2mnO
3li can deviate from gradually, there is new electrochemistry platform, thereby make the specific capacity of this material be greater than 250mAh/g, the lithium ion battery of being prepared by this material has advantages of that energy density is high;
(2) be coated in the nano-material coating on lithium-rich manganese-based anode surface and contain hole, improve the porosity of anode pole piece, strengthen the anodal embedding ability to lithium ion, thereby improve efficiency first, discharge capacity and the energy density of battery; Meanwhile, the nano-material coating that is coated in lithium-rich manganese-based anode surface can strengthen the anodal wettability to electrolyte, improves ionic conduction ability, thereby improves battery high rate performance; On the other hand, anodal surface-coated nano-material coating can improve the interface stability between positive electrode and electrolyte, electrolyte decomposition when alleviating battery and being charged to high voltage, thus make battery when thering is higher energy density, have advantages of and have extended cycle life.
(3) be coated in the nano-material coating on lithium-rich manganese-based anode surface, can intercept Li dendrite, burr etc., prevent the internal short-circuit between positive pole and negative pole, improve the security performance of battery.
(4) by adopting little electric current, stepped forming technology, can alleviate the structural change of lithium-rich manganese-based material in charge and discharge process, and battery cycle life is provided.
Claims (8)
1. take lithium-rich manganese-based material as anodal lithium ion battery for one kind, comprise positive pole, anodal face coat, negative pole, barrier film and electrolyte, it is characterized in that: described positive pole comprises positive active material 80-95%(weight ratio), conductive agent 3-18%(weight ratio), binding agent 2-17%(weight ratio), described positive active material is lithium-rich manganese-based material or the surface coated lithium-rich manganese-based material of process;
Described anodal face coat comprises nano material 85-97%(weight ratio), binding agent 3-15%(weight ratio), described nano material is one or more the combination in nano-metal-oxide, nano metal nitride, and described binding agent is a kind of in SBR and CMC combination, PVDF, PTFE, PVDF-HFP, polyacrylate;
Described negative pole comprises negative electrode active material 80-95%(weight ratio), conductive agent 3-18%(weight ratio), binding agent 2-17%(weight ratio) and, described negative electrode active material is graphite, hard carbon, soft carbon, silicon, tin, phosphorus, SnO
2, Co
3o
4, Fe
2o
3, Li
4ti
5o
12, a kind of in CuO, silicon-base alloy, kamash alloy, Mg base hydrogen bearing alloy or wherein several;
Described conductive agent is one or more the mixing in superconductive carbon black, electrically conductive graphite, flaky graphite, carbon fiber, carbon nano-tube; Described binding agent is a kind of in SBR and CMC combination, PVDF, PTFE, PVDF-HFP; Described electrolyte comprises lithium salts, organic solvent, film for additive.
2. according to claim 1ly a kind ofly take lithium-rich manganese-based material as anodal lithium ion battery, it is characterized in that: the general formula of described lithium-rich manganese-based material is xLi
2mnO
3(1-x) LiMO
2(any one in M=Mn, Ni, Co, Cr, Zn, Mg, Al, Ti), 0<x<1.
3. according to claim 1ly a kind ofly take lithium-rich manganese-based material as anodal lithium ion battery, it is characterized in that: the surperficial clad material of described surface coated lithium-rich manganese-based material is Al
2o
3, MgO, CaO, TiO
2, a kind of in ZnO, ZrO, conducting high polymers thing, carbon, Graphene or wherein several.
4. according to claim 1ly a kind ofly take lithium-rich manganese-based material as anodal lithium ion battery, it is characterized in that: the one side thickness of described anodal face coat is 1-10 μ m.
5. according to claim 1ly a kind ofly take lithium-rich manganese-based material as anodal lithium ion battery, it is characterized in that: in described anodal face coat, nano material is one or more the combination in nano aluminium oxide, nano calcium oxide, nano magnesia, nano zircite, nano zine oxide, nano-titanium oxide, nano aluminum nitride, Nano titanium nitride.
6. according to claim 1ly a kind ofly take lithium-rich manganese-based material as anodal lithium ion battery, it is characterized in that: in described anodal face coat, the average grain diameter D50 of nano material is 100-2000 nm, specific area is 2-30m
2/ g.
7. according to claim 1ly a kind ofly take lithium-rich manganese-based material as anodal lithium ion battery, it is characterized in that: the lithium salts in described electrolyte is LiPF
6, LiBF
6, LiClO
4, LiN (CF
3sO
2)
2, Li (CF
3sO
2)
3in a kind of or wherein several; Organic solvent in described electrolyte is two or more the combination in ethylene carbonate (EC), propene carbonate (PC), butylene, dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), fluorinated ethylene carbonate (FEC), glutaronitrile (CLN), adiponitrile (ADN), the first and second sulfones (EMS), methoxy ethyl methyl sulfone (MEMS); Film for additive in described electrolyte is one or both the combination in vinylene carbonate (VC), propylene sulfite (PS).
8. prepare a kind of described in claim 1-7 any one and take the method that lithium-rich manganese-based material is anodal lithium ion battery, it is characterized in that: comprise the following steps:
The preparation of anode sizing agent, cathode size comprises the following steps: by positive active material 80-95%(weight ratio), conductive agent 3-18%(weight ratio), binding agent 2-17%(weight ratio) add respectively in organic solvent, after high-speed stirred, be configured to anode sizing agent; By negative electrode active material 80-95%(weight ratio), conductive agent 3-18%(weight ratio), binding agent 2-17%(weight ratio) add respectively in organic solvent or deionized water, after high-speed stirred, be configured to cathode size;
The preparation of anodal face coat slurry comprises the following steps: by nano material 85-97%(weight ratio), binding agent 3-15%(weight ratio), add respectively in organic solvent or deionized water, after high-speed stirred, be configured to face coat slurry;
The preparation of anode pole piece, cathode pole piece comprises the following steps: anode sizing agent is coated in to aluminium foil equably by coating machine two-sided, after baking, roll-in, obtaining one side density is 5-25mg/cm
2, compacted density is 2.3-3.2g/cm
3positive plate, anodal face coat slurry is coated on the positive plate after roll-in equably, after film-making, obtain anode pole piece; Cathode size is coated in to Copper Foil equably by coating machine two-sided, after baking, roll-in, film-making, obtaining one side density is 4-12mg/cm
2, compacted density is 0.6-1.5g/ cm
3cathode pole piece;
The preparation of battery core comprises the following steps: mode that the anode pole piece preparing, cathode pole piece are replaced by positive and negative electrode is stacking or be wound into battery core, and wherein both positive and negative polarity separates with barrier film, and guarantees that Fu Liao district negative pole size is greater than anodal size; Positive and negative electrode lug is by being welded and fixed; Battery core is put into battery container, on battery container, leave electrolyte inlet; Battery core is removed moisture at 60-90 ° of C baking 12-48h;
Encapsulation fluid injection: seal liquid injection port injecting electrolyte in from electrolyte inlet to battery container;
Change into: adopt stepped charging modes to change on packaged battery, the charging voltage upper limit is controlled at 4.35-4.6V, after constant voltage is full of, transfers 4.35-4.6V constant voltage charge to, and charging current is 0.01-0.5C, along with the rising of charging voltage, reduce gradually charging current.
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