CN105336914B - Lithium ion secondary battery and lithium-rich negative plate thereof - Google Patents
Lithium ion secondary battery and lithium-rich negative plate thereof Download PDFInfo
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- CN105336914B CN105336914B CN201410309553.5A CN201410309553A CN105336914B CN 105336914 B CN105336914 B CN 105336914B CN 201410309553 A CN201410309553 A CN 201410309553A CN 105336914 B CN105336914 B CN 105336914B
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Abstract
The invention provides a lithium ion secondary battery and a lithium-rich negative plate thereof. The lithium-rich negative electrode sheet of the lithium ion secondary battery comprises: a negative current collector; and a negative electrode active material layer containing a negative electrode active material and coated on a surface of the negative electrode current collector. The surface of the negative active material layer, which is far away from the negative current collector, is coated with a lithium-containing slurry layer; the lithium-containing slurry layer comprises a dispersing agent, a conductive agent, lithium metal powder and a non-aqueous organic solvent, wherein the non-aqueous organic solvent is mutually soluble with an electrolyte of the lithium ion secondary battery. The lithium ion secondary battery comprises the lithium-rich negative electrode sheet. The lithium-rich negative plate can realize accurate, quantitative and uniform lithium enrichment, has no lithium metal powder pollution, simplifies the preparation process, and improves the lithium supplementing efficiency of the lithium-rich negative plate. The lithium ion secondary battery has higher first coulombic efficiency and rate capability, and simultaneously has lower internal resistance and self-discharge.
Description
Technical field
The present invention relates to battery technology field more particularly to a kind of lithium rechargeable battery and its rich lithium cathode sheets.
Background technology
Lithium rechargeable battery is due to advantages such as long circulation life, high voltage and high-energy densities, becoming and answering at present
With one of secondary cell widest in area.With electronic product renewal speed quickening and it is high-power, high-energy device go out
Existing, more stringent requirements are proposed for energy density of the people to lithium rechargeable battery.
Lithium rechargeable battery, due to foring solid electrolyte (SEI) film, can consume portion during first charge-discharge
Divide lithium ion, causes the reduction of effective lithium ion quantity, to reduce the capacity of lithium rechargeable battery, cause lithium ion two
The coulombic efficiency for the first time of primary cell is lower.
The patent document of 10 days 2 months Japanese Patent Application Publication Publication No. JP2005038720 in 2005 discloses one
Kind forms the method that one layer of lithium layer carries out mending lithium using the method for vacuum evaporation on negative plate surface.The lithium layer that this method obtains
Thickness is thinner than lithium piece, but the thickness of lithium layer is difficult to control, and operation must carry out in vacuum environment, and evaporation efficiency compares
Low, the transfer of follow-up negative plate is also more complex, causes the production cost of lithium rechargeable battery higher.The public affairs on the 12nd of September in 1996
The International Patent Application Publication No. opened be WO96027910 international patent documents patent disclose it is a kind of lithium piece is covered in it is negative
Naked battery core is made in pole piece winding, and the method for electrolyte is perfused later to prepare lithium rechargeable battery.Although this method
Lithium can be played the role of mending, but the amount of lithium that can absorb of negative plate is far smaller than the amount for the lithium that lithium piece is provided, therefore meeting
It causes embedding lithium uneven, and the deformation of negative plate can be caused, and then be susceptible to analysis lithium during following cycle.2012
The Chinese patent application publication No. that November 14 announced discloses a kind of using electrostatic effect for the patent document of CN102779975A
The surface that lithium metal powder should be directly sprayed at by mechanical oscillation to negative plate carries out the method for mending lithium.Although this method is simple
It is easy, but the operating process can not overcome the problems, such as that lithium metal powder is flown upward there are huge security risk, cause environment dirty
Contaminate larger, and production efficiency is relatively low.
Invention content
The problem of in view of background technology, the purpose of the present invention is to provide a kind of lithium rechargeable battery and its richnesses
Lithium cathode sheet, that the richness lithium cathode sheet can be realized is accurate, quantitative, equably rich lithium, and without lithium metal powder pollution, preparation process
It is more simplified, improve the benefit lithium efficiency of rich lithium cathode sheet, the lithium rechargeable battery have higher coulombic efficiency for the first time and
High rate performance, while there is lower internal resistance and self discharge.
To achieve the goals above, in the first aspect of the present invention, the present invention provides a kind of lithium rechargeable batteries
Rich lithium cathode sheet comprising：Negative current collector；And negative electrode active material layer, containing negative electrode active material and it is coated in cathode
The surface of collector.Pulp layer containing lithium is coated on surface of the negative electrode active material layer far from negative current collector；It is described to contain
Lithium pulp layer includes dispersant, conductive agent, lithium metal powder and non-aqueous organic solvent, wherein non-aqueous organic solvent and lithium ion
The electrolyte of secondary cell dissolves each other.
In the second aspect of the present invention, the present invention provides a kind of lithium rechargeable batteries comprising：Positive plate；Cathode
Piece；Isolation film, between positive plate and negative plate；And electrolyte.Wherein, the negative plate is according to first party of the present invention
The rich lithium cathode sheet of the lithium rechargeable battery in face.
Beneficial effects of the present invention are as follows：
1. the non-aqueous organic solvent in the pulp layer containing lithium of the present invention can dissolve each other with the electrolyte of lithium rechargeable battery,
To which the rich lithium cathode sheet after the completion of coating can form battery core without carrying out drying operation by directly winding, tradition is avoided
The problem of rich lithium layer in rich lithium technique after drying loses powder further improves the accuracy, quantitative, equal of rich lithium
Even property.
2. the non-aqueous organic solvent in the pulp layer containing lithium of the present invention can also put forward the bonding solvent swell on negative plate surface
The voidage on high negative plate surface so that there are more lithium ion tunnels between lithium metal powder, electrolyte, negative plate three,
To improve the benefit lithium efficiency of rich lithium cathode sheet, and then improve the coulombic efficiency for the first time and high rate performance of lithium rechargeable battery.
3. the preparation of the rich lithium cathode sheet of the present invention need to only carry out in dry environment, the requirement to equipment is low, prepares work
Skill is simple, environmental-friendly, slurry containing lithium easily shifts, production efficiency is high, cost of investment is low, is suitble to large-scale industrial production.
Specific implementation mode
The following detailed description of lithium rechargeable battery according to the present invention and its rich lithium cathode sheet and embodiment, comparative example
And test result.
Illustrate the rich lithium cathode sheet of lithium rechargeable battery according to a first aspect of the present invention first.
The rich lithium cathode sheet of lithium rechargeable battery according to a first aspect of the present invention, including：Negative current collector；And it is negative
Pole active material layer, the surface containing negative electrode active material and coated in negative current collector.The negative electrode active material layer is separate
Pulp layer containing lithium is coated on the surface of negative current collector；The pulp layer containing lithium includes dispersant, conductive agent, lithium metal powder
And non-aqueous organic solvent, the electrolyte of wherein non-aqueous organic solvent and lithium rechargeable battery dissolve each other.
When lithium slurry will be contained coated on surface of the negative electrode active material layer far from negative current collector, due to lithium metal powder
The density at end is small, only 0.534g/cm3, it is easy to float in slurry containing lithium.In coating procedure, due to lithium metal powder
Floating can lead to the separation of non-aqueous organic solvent and solid component.And with the progress of coating procedure, slurry containing lithium is dried, and leads
Cause coating procedure that can not carry out.Non-aqueous organic solvent in the pulp layer containing lithium of the present invention can be with the electricity of lithium rechargeable battery
Solution liquid dissolve each other, to coating after the completion of rich lithium cathode sheet can by directly winding be formed battery core without carry out drying operation,
Avoid the problem of rich lithium layer in traditional rich lithium technique after drying loses powder；Meanwhile it is non-aqueous in pulp layer containing lithium
The bonding solvent swell on negative plate surface can also be improved the voidage on negative plate surface by organic solvent so that lithium metal powder,
There are more lithium ion tunnels between electrolyte, negative plate three, to promote the benefit lithium efficiency of rich lithium cathode sheet, and then improves
The coulombic efficiency for the first time and high rate performance of lithium rechargeable battery.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the negative current collector
It can be porous current collector.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the negative electrode active material
Negative electrode active material in matter layer can be selected from graphite, silicon, SiOx(0<x<One or more of 2).
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the pulp layer containing lithium
Thickness can be 10 μm~120 μm.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the slurry containing lithium exists
Coating method on the negative current collector can be selected from silk-screen printing, rotogravure application, extruding (Slot-die) coating, transfer coating
In one kind.In one embodiment, when using silk-screen printing, non-aqueous organic solvent may be used high boiling non-aqueous organic molten
Thus agent prevents slurry containing lithium to be air-dried on printing screen plate, so as to providing excellent printing quality.The height boiling
The boiling point of the non-aqueous organic solvent of point can be more than 90 DEG C, can preferably be more than 100 DEG C.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the dispersant can be
Non-ionic (polymeric surfactant), the dispersant can be used for stablizing the slurry containing lithium.When using silk-screen printing, institute
Dispersant is stated to cannot be only used for stablizing the slurry containing lithium but also slurry containing lithium can be fixed on to the site position on negative plate surface
It sets.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the nonionic is high
The HLB value of molecular surface active agent can be 10~18.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the nonionic is high
The weight average molecular weight of molecular surface active agent can be 800~1300000.If the weight of non-ionic (polymeric surfactant) is equal
Molecular weight is too low, then needs that stable slurry containing lithium could be formed compared with multi-dispersant in slurry containing lithium, and more dispersant meeting
Lithium metal powder tight is got up, the capacity of lithium is hindered to play, reduces the quantity and electron conduction of lithium ion tunnel, and
And the weight average molecular weight of non-ionic (polymeric surfactant) is too low, then its strand is shorter, cannot function well as space
Steric hindrance.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the nonionic is high
Molecular surface active agent can contain polar group, the polar group can be selected from amino, hydroxyl, amide groups, ether, carboxyl and
One or more of halogen.The polar group carries positive charge or negative electrical charge because forming difference, when the polar group
When with negative electrical charge, it can be linked together by electrostatic attraction effect with the positively charged lithium metal powder in surface；When the pole
Property group when carrying positive charge, can due to electrostatic repulsion and can far from surface positively charged lithium metal powder, from rather than
The strand of ionic high molecular surfactant can form steric hindrance between the particle of lithium metal powder, to contribute to
Form stable slurry containing lithium.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the nonionic is high
Molecular surface active agent can be selected from polyalcohols, polyethers, Kynoar, polyacrylic acid and its derivative, ethylene oxide and epoxy third
Alkyl copolymer, the ring opening copolymer zoarium of cyclic imino ether, polyvinyl lactams, one kind in cellulose and its derivates or several
Kind.
It is specifically, described non-in the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention
Ionic high molecular surfactant can be selected from polyethylene glycol oxide (PEO), polyvinyl alcohol (PVA), polyvinylpyrrolidone
(PVP), one kind in vinylpyrrolidone graft copolymer (Agrimer AL10) and hydroxypropyl methyl cellulose (HPMC)
Or it is several.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the conductive agent is optional
Preferably can be carbon material from one or more of carbon material, conducting polymer, metal and metal oxide.The conduction
Agent can prevent the fully wrapped around lithium metal powder of dispersant, and the capacity to be conducive to lithium plays.When conductive agent is carbon material,
Since the carbon atom of carbon material uses SP2 hydridization, surface to carry negative electrical charge, it can be acted on by electrostatic attraction and be adsorbed on lithium gold
The surface for belonging to powder avoids lithium metal powder from being wrapped up completely by dispersant to form conductive layer；And the presence of carbon material
Enough electron channels are provided, the probability that electrolyte is contacted with lithium metal powder is increased, so as to save traditional rich lithium
Calandering steps in technique.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the carbon material is optional
Self-conductive carbon black SP, electrically conductive graphite KS-6, electrically conductive graphite SFG-6, Ketjen black EC300J, Ketjen black ECP, Ketjen black ECP-
One or more of 600JD, carbon nanotube (CNT) and vapor-grown carbon fibers (VGCF), graphene (Graphene), it is excellent
Choosing can be conductive carbon black SP.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the conducting polymer
Can be selected from polythiophene (PTH), polyaniline (PANI), polypyrrole (PPy), polyacetylene (PA), one kind in polyphenylacetylene (PPV) or
It is several.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the metal can be selected from
One or more of Ag, Au, Ca, Cr, Ni, Mn, Sn, Zn.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the metal oxide
It can be selected from vanadium oxide (V2O5), tin oxide (SnO2), one or more of zinc oxide (ZnO).
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the lithium metal powder
Can be spherical shape, the mean particle size D50 of the lithium metal powder can be 5 μm~100 μm, preferably can be 20 μm~50 μm.
It is described non-aqueous organic molten in the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention
Agent can be selected from one or more of aromatic hydrocarbon, alicyclic, halogenated hydrocarbons, esters, ketone, preferably can be carbonic ester.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the carbonic ester is optional
From ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and dibutyl carbonate
One or more of (DBC).
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the weight of the dispersant
Amount can be the 0.2%~5% of the total weight of the pulp layer containing lithium.When the content of dispersant is less than 0.2%, cannot play
Dispersion and the effect for stablizing the slurry containing lithium be easy to cause lithium metal powder and float in slurry containing lithium and lead to slurry containing lithium point
Layer；When the content of dispersant is more than 5%, the electric conductivity of negative plate can be deteriorated, and the capacity to be unfavorable for lithium plays.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the weight of the conductive agent
Amount can be the 0.1%~10% of the total weight of the pulp layer containing lithium.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the lithium metal powder
Weight can be the pulp layer containing lithium total weight 16%~50%.When the content of lithium metal powder is less than 16%, bear
The amount of the lithium metal printed on pole piece is not enough to achieve the effect that benefit lithium, i.e., cannot play the lithium during making up first charge-discharge
Consumption effect, and the manufacturing cost of lithium rechargeable battery can be increased, and cause lithium rechargeable battery internal resistance and
Polarized increase；When the content of lithium metal powder is more than 50%, since the density of lithium metal is small, volume is big, it is difficult into
The stirring of row slurry containing lithium.
It is described non-aqueous organic molten in the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention
The weight of agent can be the 40%~70% of the total weight of the pulp layer containing lithium.When the content of non-aqueous organic solvent is less than 30%
When, the viscosity of the slurry containing lithium is higher, and solid content is too high, causes not being stirred；When the content of non-aqueous organic solvent is more than
When 80%, the viscosity of the slurry containing lithium is too low, is easy to cause material leakage, and coating is caused to be not easy to carry out, or the slurry containing lithium of coating is turning
Flowing is easy during moving, the uniformity of the pulp layer containing lithium resulted in is poor.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the pulp layer containing lithium
It may also include one or more of non-lithium oxide powder, the non-oxidate for lithium can be selected from SiO2、HfO2、SrTiO3、
SnO2、CeO2、MgO、NiO、CaO、ZnO、ZrO2、Y2O3、Al2O3、TiO2One or more of, to improve touching for the slurry containing lithium
Denaturation, is conducive to the uniform coating of the slurry containing lithium.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the non-oxidate for lithium
The weight of powder can be the 0.1%~10% of the total weight of the pulp layer containing lithium.
In the rich lithium cathode sheet of the lithium rechargeable battery described according to a first aspect of the present invention, the lithium ion secondary
The electrolyte of battery can be selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), propene carbonate (PC), ethylene carbonate
(EC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), carbonic acid first isopropyl ester (MiPC), 1,4- butyrolactone (GBL), diformazan
Base tetrahydrofuran (2Me-THF), tetrahydrofuran (THF), butylene (BC), 1,2- dimethoxy-ethanes (DME), carbonic acid two
Butyl ester (DBC), carbonic acid first butyl ester (BMC), dipropyl carbonate (DPC), methyl esters (PA), ethyl acetate (MA), methyl formate (MF),
One or more of methyl propionate (MP).
Secondly the lithium rechargeable battery of explanation according to a second aspect of the present invention.
Lithium rechargeable battery according to a second aspect of the present invention, including：Positive plate；Negative plate；Isolation film is located at anode
Between piece and negative plate；And electrolyte.Wherein, the negative plate is the lithium rechargeable battery according to first aspect present invention
Rich lithium cathode sheet.
Will be illustrated next lithium rechargeable battery according to the present invention and its rich lithium cathode sheet and embodiment and comparative example.
Embodiment 1
1. the preparation of the initial negative plate of lithium rechargeable battery
By negative electrode active material graphite and SiOx(0<x<2) mixture (weight ratio 1:1, the gram volume of graphite is
340mAh/g, for the first time coulombic efficiency are 91%, SiOx(0<x<2) gram volume is 1135mAh/g, coulombic efficiency is for the first time
58.4%), (specific surface area BET is 62m by bonding agent butadiene-styrene rubber, conductive agent conductive carbon black SP2/ g) in mass ratio 92:3:5 with
Solvent N-methyl pyrilidone (NMP) is uniformly mixed and negative electrode slurry is made, later according to 121mg/1540mm2Coat weight will
Negative electrode slurry is coated uniformly on the tow sides of porous current collector copper foil, and cathode membrane is formed after then being dried at 85 DEG C,
And the water content of cathode membrane is no more than 300ppm, is then cold-pressed, trimming, cut-parts, slitting, welds negative lug, obtains
Width is the initial negative plate of the lithium rechargeable battery of 160mm.
2. the preparation of the rich lithium cathode sheet of lithium rechargeable battery
By dispersant polyethylene glycol oxide (PEO, HLB value 14, weight average molecular weight 600000), conductive agent conductive carbon black SP
(specific surface area BET is 62m2/ g), lithium metal powder (D50 be 40 μm), non-aqueous organic solvent propene carbonate (PC), carbonic acid second
Mixture (the weight ratio 3 of enester (EC) and diethyl carbonate (DEC):2:3) by weight 0.6:0.4:30:69 mixing are equal
It is even, slurry containing lithium is obtained, the slurry containing lithium of gained is coated in the table of the initial negative plate of gained with screen printing technique later
Face obtains the rich lithium cathode sheet of lithium rechargeable battery, wherein slurry containing lithium forms slurry containing lithium after the drying after dry
The thickness of layer, the pulp layer containing lithium is 60 μm, and the spacing of pulp layer containing lithium in spot distribution and between points is 100 μm.
3. the preparation of the positive plate of lithium rechargeable battery
By positive active material cobalt acid lithium (LiCoO2), binder Kynoar (PVDF), conductive agent conductive carbon black SP
(specific surface area BET is 62m2/ g) in mass ratio 97:1.5:1.5 are dissolved in solvent N-methyl pyrilidone (NMP), stir evenly
Anode sizing agent is made, then anode sizing agent is uniformly coated on positive and negative two surfaces of plus plate current-collecting body aluminium foil, later 85
At DEG C dry after obtain the positive diaphragm of 118 μ m-thicks, later by cold pressing, slice, slitting, weld positive pole ear, obtain lithium from
The positive plate of sub- secondary cell.
4. the preparation of the electrolyte of lithium rechargeable battery
By lithium salts LiPF6With non-aqueous organic solvent (ethylene carbonate (EC):Diethyl carbonate (DEC):Methyl ethyl carbonate
(EMC):Vinylene carbonate (VC)=8:85:5:2, mass ratio) in mass ratio 8:92 solution being formulated are as lithium ion
The electrolyte of secondary cell.
5. the preparation of lithium rechargeable battery
After positive plate, isolation film (PE films) and rich lithium cathode sheet winding, naked battery core is obtained, later by encapsulation, note
Enter electrolyte, chemical conversion, pumping molding obtains lithium rechargeable battery.
Embodiment 2
Lithium rechargeable battery is prepared according to the method for embodiment 1, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, non-aqueous organic solvent is that the mixture of propene carbonate (PC) and dimethyl carbonate (DMC) (weighs
Amount is than being 3:2), dispersant:Conductive agent:Lithium metal powder:The weight ratio of non-aqueous organic solvent is 0.2:0.8:30:69.
Embodiment 3
Lithium rechargeable battery is prepared according to the method for embodiment 1, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, non-aqueous organic solvent be propene carbonate (PC) and ethylene carbonate (EC) mixture (weight
Than being 1:3), dispersant:Conductive agent:Lithium metal powder:The weight ratio of non-aqueous organic solvent is 0.6:0.1:30:69.3.
Embodiment 4
Lithium rechargeable battery is prepared according to the method for embodiment 1, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, non-aqueous organic solvent is that the mixture of diethyl carbonate (DEC) and propene carbonate (PC) (weighs
Amount is than being 2:3), dispersant:Conductive agent:Lithium metal powder:The weight ratio of non-aqueous organic solvent is 0.4:0.6:30:69.
Embodiment 5
Lithium rechargeable battery is prepared according to the method for embodiment 1, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, dispersant is polyvinyl alcohol (PVA), and HLB value 12, weight average molecular weight 16000 is non-aqueous to have
Solvent is propene carbonate (PC).
Embodiment 6
Lithium rechargeable battery is prepared according to the method for embodiment 5, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, dispersant is polyvinylpyrrolidone (PVP), and HLB value 17, weight average molecular weight is
1300000。
Embodiment 7
Lithium rechargeable battery is prepared according to the method for embodiment 6, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, conductive carbon be carbon nanotube CNT, average diameter 11nm, average length be 10 μm, specific surface
Product BET is 240m2/g。
Embodiment 8
Lithium rechargeable battery is prepared according to the method for embodiment 6, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, conductive carbon is electrically conductive graphite KS-6, and D50 is 5 μm, and specific surface area BET is 20m2/g。
Embodiment 9
Lithium rechargeable battery is prepared according to the method for embodiment 7, only in the initial negative plate of lithium rechargeable battery
Preparation (i.e. step (1)) in, negative electrode active material is graphite.
Embodiment 10
Lithium rechargeable battery is prepared according to the method for embodiment 7, only in the initial negative plate of lithium rechargeable battery
Preparation (i.e. step (1)) in, negative electrode active material is the mixture of graphite and silicon, and the weight ratio of the two is 3:1, wherein silicon
Gram volume be 3800mAh/g, coulombic efficiency is 62% for the first time.
Embodiment 11
Lithium rechargeable battery is prepared according to the method for embodiment 7, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, dispersant is that (AgrimerAL10, HLB value 18, weight are equal for vinylpyrrolidone graft copolymer
Molecular weight is that 1000000), non-aqueous organic solvent is the mixture (weight ratio of propene carbonate (PC) and ethylene carbonate (EC)
It is 1:3), dispersant:Conductive agent:Lithium metal powder:The weight ratio of non-aqueous organic solvent is 5:5:50:40.
Embodiment 12
Lithium rechargeable battery is prepared according to the method for embodiment 1, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, dispersant be hydroxypropyl methyl cellulose (HPMC, HLB value 10, weight average molecular weight 800),
Non-aqueous organic solvent is that (weight ratio is for the mixture of dimethyl carbonate (DMC), ethylene carbonate (EC) and propene carbonate (PC)
4:2:3), dispersant:Conductive agent:Lithium metal powder:The weight ratio of non-aqueous organic solvent is 5:10:16:69.
Embodiment 13
Lithium rechargeable battery is prepared according to the method for embodiment 4, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, in slurry containing lithium also contain non-lithium oxide powder, non-lithium oxide powder be Al2O3(grain size
For 30nm, specific surface area 150m2/ g), dispersant:Conductive agent:Lithium metal powder:Non- lithium oxide powder:It is non-aqueous organic molten
The weight ratio of agent is 0.4:0.6:30:1:68.
Embodiment 14
Lithium rechargeable battery is prepared according to the method for embodiment 13, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, in slurry containing lithium also contain non-lithium oxide powder, non-lithium oxide powder be TiO2, grain size
For 30nm, specific surface area 150m2/g。
Embodiment 15
Lithium rechargeable battery is prepared according to the method for embodiment 13, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, in slurry containing lithium also contain non-lithium oxide powder, non-lithium oxide powder be SiO2, grain size
For 50nm, specific surface area 120m2/g。
Embodiment 16
Lithium rechargeable battery is prepared according to the method for embodiment 15, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in dispersant:Conductive agent:Lithium metal powder:Non- lithium oxide powder:The weight of non-aqueous organic solvent
Than being 0.4:0.6:30:2:67.
Embodiment 17
Lithium rechargeable battery is prepared according to the method for embodiment 15, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, dispersant:Conductive agent:Lithium metal powder:Non- lithium oxide powder:The weight of non-aqueous organic solvent
Amount is than being 0.4:0.6:30:6:63.
Embodiment 18
Lithium rechargeable battery is prepared according to the method for embodiment 15, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, dispersant:Conductive agent:Lithium metal powder:Non- lithium oxide powder:The weight of non-aqueous organic solvent
Amount is than being 0.4:0.6:30:10:59.
Embodiment 19
Lithium rechargeable battery is prepared according to the method for embodiment 15, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, dispersant:Conductive agent:Lithium metal powder:Non- lithium oxide powder:The weight of non-aqueous organic solvent
Amount is than being 0.4:0.6:30:0.1:68.9.
Comparative example 1
Lithium rechargeable battery is prepared according to the method for embodiment 1, only in the rich lithium cathode sheet of lithium rechargeable battery
Preparation (i.e. step (2)) in, be added without conductive agent, dispersant:Lithium metal powder:The weight ratio of non-aqueous organic solvent is 0.6:
30:69.4。
Finally illustrate the test process and test knot of lithium rechargeable battery according to the present invention and its rich lithium cathode sheet
Fruit.
1. the weight variation coefficient of the pulp layer containing lithium
Use precision for the weight (being denoted as A) of the initial negative plate of the electronic balance weighing of 0.001g, initial negative plate single side
The weight (being denoted as B) after pulp layer containing lithium, the weight (being denoted as C) after initial negative plate dual coating pulp layer containing lithium are coated, then
Initial negative plate single side net coated weight WS=B-A, the initial two-sided net coated weight WD=C-A of negative plate.
In formula (1)~(4), n is sampling number of samples, herein n=50.
Weight variation coefficient (%)=single side standard deviation/single side mean value × 100% of single side coating；
Weight variation coefficient (%)=two-sided standard deviation/two-sided mean value × 100% of dual coating.
2. the analysis lithium test of rich lithium cathode sheet
The rich lithium cathode sheet surface analysis lithium of observation is serious and uniformity coefficient, wherein analysis lithium degree be divided into slight analysis lithium, analysis lithium with
And seriously analyse lithium.Slight analysis lithium indicates that the analysis lithium region of membrane surface is less than 20%, and analysis lithium indicates the analysis lithium region of membrane surface
It is 20%~70%, serious lithium of analysing indicates that the analysis lithium region of membrane surface is more than 70%.
3. the bending picking test of rich lithium cathode sheet
By rich lithium cathode sheet doubling, observe whether the diaphragm at doubling folding line falls off from porous current collector.Wherein
The area that diaphragm at "None" expression doubling folding line falls off from porous current collector is less than 5%, at " slight " expression doubling folding line
The area that falls off from porous current collector of diaphragm be 5%~50%, the diaphragm at " serious " expression doubling folding line is from porous collection
The area to fall off on fluid is more than 50%.
4. the volume test of lithium rechargeable battery
At 25 DEG C, 3.9V is first charged to lithium rechargeable battery with the constant current of 0.02C multiplying powers, this charging
Capacity is denoted as ICC0, then charges to 4.4V to lithium rechargeable battery with the constant current of 0.5C multiplying powers, this charging is held
Amount is denoted as AGC0, is then discharged to 3.0V to lithium rechargeable battery with the constant current of 0.7C multiplying powers, this discharge capacity
It is denoted as D0.
The coulombic efficiency for the first time (%) of lithium rechargeable battery=D0/ (ICC0+AGC0) × 100%.
5. the internal resistance (IMP) of lithium rechargeable battery is tested
The impedance of lithium rechargeable battery on ac impedance measurement instrument after test capacity test, when test, are used
Frequency is 1000Hz.
6. the high rate performance of lithium rechargeable battery is tested
Lithium rechargeable battery after volume test is completely filled, is carried out respectively with the constant current of 0.2C and 2C multiplying powers later
Electric discharge, records respective discharge capacity D1 and D2.
2C/0.2C high rate performances (%)=D2/D1 × 100% of lithium rechargeable battery.
7. the self discharge (K values) of lithium rechargeable battery is tested
Lithium rechargeable battery after volume test is transferred in 45 DEG C of oven and is toasted for 24 hours, later by lithium ion
Secondary cell takes out and stands at room temperature and tests the open-circuit voltage of lithium rechargeable battery for 24 hours and be denoted as OCV1；Again by lithium ion
Secondary cell stands 72h at room temperature, and the open-circuit voltage for testing lithium rechargeable battery is denoted as OCV2.
Voltage drop (i.e. K values)=OCV1-OCV2 of lithium rechargeable battery.
Table 1 provides the parameter and the performance test results of embodiment 1-19 and comparative example 1.
Next the performance test results of embodiment 1-19 and comparative example 1 are analyzed.
As can be seen that the lithium ion of the rich lithium cathode sheet using the present invention from the comparison of embodiment 1-19 and comparative example 1
The internal resistance (IMP) and self discharge (K values) of secondary cell do not obviously increase, and the coulombic efficiency for the first time of lithium rechargeable battery and
High rate performance is obviously improved.This is because the non-aqueous organic solvent in the pulp layer containing lithium of the present invention can be by negative plate table
The bonding solvent swell in face improves the voidage on negative plate surface so that have between lithium metal powder, electrolyte, negative plate three
More lithium ion tunnels to promote the benefit lithium efficiency of negative plate, and then improve the effect of coulomb for the first time of lithium rechargeable battery
Rate and high rate performance.
It can also be seen that the weight percentage with conductive agent increases from the comparison of embodiment 1 and embodiment 3, lithium
The coulombic efficiency for the first time and high rate performance of ion secondary battery increase.
It is from the comparison of embodiment 1 and embodiment 5-6 as can be seen that electric as the lithium ion secondary of dispersant using PEO
The coulombic efficiency for the first time and high rate performance in pond are than the coulomb for the first time using PVA and PVP as the lithium rechargeable battery of dispersant
Efficiency and high rate performance will be got well.This is because PEO has the ability of stronger dissociation lithium salts relative to PVA and PVP, and to lithium
Stablize；In the charge and discharge process of lithium rechargeable battery, oxygen atom in lithium ion and PEO by coordination constantly into
Row complexing and dissociation, to be conducive to lithium ion in the fast transferring of inside battery, and then the coulombic efficiency for the first time and multiplying power of PEO
Performance goes with PVP compared with PVA.
As can be seen that the specific surface area with conductive agent increases from the comparison of embodiment 6-8, lithium rechargeable battery
Coulombic efficiency reduces for the first time, but the high rate performance of lithium rechargeable battery increases.This is because when the specific surface area of conductive agent
When increase, conductive agent particle has more probabilities to be contacted with the surface of lithium metal powder, and provides more electron channels, to
Increase the migration rate of electronics, and then improves the high rate performance of lithium rechargeable battery；But the specific surface area of conductive agent increases
Afterwards, in formation process, conductive agent particle surface can form more SEI films, and then consume more lithiums, thus cause lithium from
The coulombic efficiency for the first time of sub- secondary cell reduces.
From in the comparison of embodiment 4 and embodiment 13-19 as can be seen that add into slurry containing lithium non-oxidate for lithium can be with
Improve the thixotropy of the slurry containing lithium, improves dispersion effect of each solid component in slurry containing lithium in non-aqueous organic solvent, into
And the uniformity of the coating of slurry containing lithium is improved, and be embodied in the reduction of the weight variation coefficient of the pulp layer containing lithium, i.e., it is coated
The weight consistency of Cheng Zhong, the pulp layer containing lithium improve.
It can also be seen that using TiO from the comparison of embodiment 13-152Lithium ion secondary electricity as non-oxidate for lithium
Coulombic efficiency for the first time and the high rate performance ratio in pond use Al2O3And SiO2The head of lithium rechargeable battery as non-oxidate for lithium
Secondary coulombic efficiency and high rate performance will be got well.This is because TiO2Removal lithium embedded invertibity is preferable, structural stability is high, Neng Gouti
For more lithium ion tunnel and larger embedding lithium capacity.
From the comparison of embodiment 15-19 it can also be seen that with SiO2Weight percentage increase, lithium ion secondary
The high rate performance of battery increases, and the internal resistance (IMP) of lithium rechargeable battery reduces.This is because the SiO in pulp layer containing lithium2
The increase of weight percentage can improve the thixotropy and impressionability of the slurry containing lithium, make slurry containing lithium dispersedly evenly,
So that film is evenly, and then the weight consistency of the pulp layer containing lithium improves, the internal resistance of final lithium rechargeable battery
(IMP) it reduces；The uniformity increase of film can reduce the migration resistance of lithium ion, and then it is preferable so that lithium rechargeable battery is had
High rate performance.
Claims (11)
1. a kind of rich lithium cathode sheet of lithium rechargeable battery, including：
Negative current collector；And
Negative electrode active material layer, the surface containing negative electrode active material and coated in negative current collector；
It is characterized in that,
Pulp layer containing lithium is coated on surface of the negative electrode active material layer far from negative current collector；
The pulp layer containing lithium includes dispersant, conductive agent, lithium metal powder and non-aqueous organic solvent, wherein non-aqueous organic molten
The electrolyte of agent and lithium rechargeable battery dissolves each other；
The conductive agent is selected from carbon material, and the carbon atom of carbon material is SP2 hydridization；
The weight of the non-aqueous organic solvent is the 40%~70% of the total weight of the pulp layer containing lithium.
2. the rich lithium cathode sheet of lithium rechargeable battery according to claim 1, which is characterized in that the dispersant is non-
Ionic high molecular surfactant, the non-ionic (polymeric surfactant) contain polar group, the polar group
Selected from one or more of amino, hydroxyl, amide groups, ether, carboxyl and halogen.
3. the rich lithium cathode sheet of lithium rechargeable battery according to claim 2, which is characterized in that the nonionic is high
Molecular surface active agent is selected from polyalcohols, polyethers, Kynoar, polyacrylic acid and its derivative, ethylene oxide and propylene oxide
Ring opening copolymer zoarium, polyvinyl lactams and one kind or several in cellulose and its derivates of copolymer, cyclic imino ether
Kind.
4. the rich lithium cathode sheet of lithium rechargeable battery according to claim 1, which is characterized in that the lithium metal powder
Average grain diameter D50 for spherical shape, the particle of the lithium metal powder is 5 μm~100 μm.
5. the rich lithium cathode sheet of lithium rechargeable battery according to claim 4, which is characterized in that the lithium metal powder
Particle average grain diameter D50 be 20 μm~50 μm.
6. the rich lithium cathode sheet of lithium rechargeable battery according to claim 1, which is characterized in that described non-aqueous organic molten
Agent is selected from one or more of aromatic hydrocarbon, alicyclic, halogenated hydrocarbons, esters, ketone.
7. the rich lithium cathode sheet of lithium rechargeable battery according to claim 6, which is characterized in that described non-aqueous organic molten
Agent is carbonic ester.
8. the rich lithium cathode sheet of lithium rechargeable battery according to claim 1, which is characterized in that
The weight of the dispersant is the 0.2%~5% of the total weight of the pulp layer containing lithium；
The weight of the conductive agent is the 0.1%~10% of the total weight of the pulp layer containing lithium；
The weight of the lithium metal powder is the 16%~50% of the total weight of the pulp layer containing lithium.
9. the rich lithium cathode sheet of lithium rechargeable battery according to claim 1, which is characterized in that the pulp layer containing lithium
Further include non-lithium oxide powder, the non-oxidate for lithium is selected from SiO2、HfO2、SrTiO3、SnO2、CeO2、MgO、NiO、CaO、
ZnO、ZrO2、Y2O3、Al2O3、TiO2One or more of, the weight of the non-lithium oxide powder is the pulp layer containing lithium
Total weight 0.1%~10%.
10. the rich lithium cathode sheet of lithium rechargeable battery according to claim 1, which is characterized in that the lithium ion two
The electrolyte of primary cell is selected from dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, methyl ethyl carbonate, carbonic acid
First propyl ester, carbonic acid first isopropyl ester, 1,4- butyrolactone, dimethyl-tetrahydrofuran, tetrahydrofuran, butylene, 1,2- dimethoxies
Base ethane, dibutyl carbonate, carbonic acid first butyl ester, dipropyl carbonate, ethyl acetate, methyl formate, one kind in methyl propionate or
It is several.
11. a kind of lithium rechargeable battery, including：
Positive plate；
Negative plate；
Isolation film, between positive plate and negative plate；And
Electrolyte；
It is characterized in that, the negative plate is the rich lithium of the lithium rechargeable battery according to any one of claim 1-10
Negative plate.
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