CN105336914A - 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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- CN105336914A CN105336914A CN201410309553.5A CN201410309553A CN105336914A CN 105336914 A CN105336914 A CN 105336914A CN 201410309553 A CN201410309553 A CN 201410309553A CN 105336914 A CN105336914 A CN 105336914A
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- 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
Abstract
The invention provides a lithium ion secondary battery and a lithium-rich negative plate thereof. The lithium-rich negative plate of the lithium ion battery comprises a negative current collector and a negative active substance layer, wherein the negative active substance layer contains a negative active substance and covers the surface of the negative current collector; the surface, far away from the negative current collector, of the negative active substance layer 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 and an electrolyte solution of the lithium ion secondary battery are mutually dissolved. The lithium ion secondary battery comprises the lithium-rich negative plate. The lithium-rich negative plate provided by the invention can realize accurate, quantitative and uniform lithium enrichment, and is free of lithium metal powder pollution, so that the preparation technology is simpler, and the lithium supplementing efficiency of the lithium-rich negative plate is improved. The lithium ion secondary battery provided by the invention has higher first coulombic efficiency and rate performance, and also has lower resistance and self-discharge.
Description
Technical field
The present invention relates to cell art, particularly relate to a kind of lithium rechargeable battery and rich lithium cathode sheet thereof.
Background technology
Lithium rechargeable battery, owing to having the advantages such as long circulation life, high voltage and high-energy-density, becomes one of the widest secondary cell of current range of application.Along with quickening and the appearance that is high-power, high-energy device of electronic product renewal speed, the energy density of people to lithium rechargeable battery is had higher requirement.
Lithium rechargeable battery is in first charge-discharge process, owing to defining solid electrolyte (SEI) film, part lithium ion can be consumed, cause the reduction of effective lithium ion quantity, thus reduce the capacity of lithium rechargeable battery, cause the step-down of coulombic efficiency first of lithium rechargeable battery.
Japanese Unexamined Patent Publication No disclosed in 10 days February in 2005 is that a kind of method of vacuum evaporation that adopts that patent document discloses of JP2005038720 forms on negative plate surface the method that one deck lithium layer carries out mending lithium.The Thickness Ratio lithium sheet of the lithium layer that the method obtains is thin, but the thickness of lithium layer is difficult to control, and operation must be carried out in vacuum environment, and evaporation efficiency is lower, and the transfer of follow-up negative plate is also more complicated, causes the production cost of lithium rechargeable battery higher.International Patent Application Publication No. disclosed in 12 days September in 1996 is that the international patent documents of WO96027910 patent discloses a kind of negative plate surface winding that covered by lithium sheet and makes naked battery core, pours into the method for electrolyte afterwards to prepare lithium rechargeable battery.Although the method also can play the effect of mending lithium, but the amount of the lithium that negative plate can absorb is far smaller than the amount of the lithium that lithium sheet provides, therefore embedding lithium can be caused uneven, and the distortion of negative plate can be caused, and then easily occur analysing lithium in following cycle process.The Chinese patent application publication No. announced on November 14th, 2012 be CN102779975A patent document discloses a kind of method adopting electrostatic effect to carry out the surface that lithium metal powder is directly sprayed at negative plate by mechanical oscillation to mend lithium.Although the method is simple, there is huge potential safety hazard in this operating process, cannot overcome the problem that lithium metal powder flies upward, and cause environmental pollution comparatively large, and production efficiency is also lower.
Summary of the invention
In view of Problems existing in background technology, the object of the present invention is to provide a kind of lithium rechargeable battery and rich lithium cathode sheet thereof, described rich lithium cathode sheet can realize accurately, quantitatively, rich lithium equably, and pollute without lithium metal powder, preparation technology more simplifies, improve the benefit lithium efficiency of rich lithium cathode sheet, described lithium rechargeable battery has higher coulombic efficiency first and high rate performance, has lower internal resistance and self discharge simultaneously.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of rich lithium cathode sheet of lithium rechargeable battery, it comprises: negative current collector; And negative electrode active material layer, be coated in the surface of negative current collector containing negative electrode active material.Described negative electrode active material layer is away from the surface of negative current collector being coated with containing lithium pulp layer; The described lithium pulp layer that contains comprises dispersant, conductive agent, lithium metal powder and non-aqueous organic solvent, and wherein the electrolyte of non-aqueous organic solvent and lithium rechargeable battery dissolves each other.
In a second aspect of the present invention, the invention provides a kind of lithium rechargeable battery, it comprises: positive plate; Negative plate; Barrier film, between positive plate and negative plate; And electrolyte.Wherein, described negative plate is the rich lithium cathode sheet of lithium rechargeable battery according to a first aspect of the present invention.
Beneficial effect of the present invention is as follows:
1. the non-aqueous organic solvent contained in lithium pulp layer of the present invention can dissolve each other with the electrolyte of lithium rechargeable battery, thus the rich lithium cathode sheet after having applied directly can be reeled and formed battery core and do not need to carry out drying operation, there is the problem of dry linting in the rich lithium layer avoided in traditional rich lithium technique after drying, further increases the accuracy of rich lithium, quantitative, uniformity.
2. the non-aqueous organic solvent contained in lithium pulp layer of the present invention can also by swelling for the bonding agent on negative plate surface, improve the voidage on negative plate surface, make there is more lithium ion tunnel between lithium metal powder, electrolyte, negative plate three, thus improve the benefit lithium efficiency of rich lithium cathode sheet, and then improve coulombic efficiency first and the high rate performance of lithium rechargeable battery.
3. the preparation of rich lithium cathode sheet of the present invention only need be carried out in dry environment, preparation technology low to the requirement of equipment is simple, environmental friendliness, easily shift containing lithium slurry, production efficiency is high, cost of investment is low, is applicable to large-scale industrial production.
Embodiment
The following detailed description of lithium rechargeable battery according to the present invention and rich lithium cathode sheet thereof and embodiment, comparative example and test result.
First the rich lithium cathode sheet of lithium rechargeable battery is according to a first aspect of the present invention described.
The rich lithium cathode sheet of lithium rechargeable battery according to a first aspect of the present invention, comprising: negative current collector; And negative electrode active material layer, be coated in the surface of negative current collector containing negative electrode active material.Described negative electrode active material layer is away from the surface of negative current collector being coated with containing lithium pulp layer; The described lithium pulp layer that contains comprises dispersant, conductive agent, lithium metal powder and non-aqueous organic solvent, and wherein the electrolyte of non-aqueous organic solvent and lithium rechargeable battery dissolves each other.
By containing lithium slurry be coated in negative electrode active material layer away from the surface of negative current collector time, because the density of lithium metal powder is little, be only 0.534g/cm
3, it is easily floating containing in lithium slurry.In coating procedure, the floating due to lithium metal powder can cause being separated of non-aqueous organic solvent and solid constituent.And along with the carrying out of coating procedure, become dry containing lithium slurry, cause coating procedure to carry out.The non-aqueous organic solvent contained in lithium pulp layer of the present invention can dissolve each other with the electrolyte of lithium rechargeable battery, thus the rich lithium cathode sheet after having applied directly can be reeled and forms battery core and do not need to carry out drying operation, there is the problem of dry linting in the rich lithium layer avoided in traditional rich lithium technique after drying; Simultaneously, can also by swelling for the bonding agent on negative plate surface containing the non-aqueous organic solvent in lithium pulp layer, improve the voidage on negative plate surface, make there is more lithium ion tunnel between lithium metal powder, electrolyte, negative plate three, thus promote the benefit lithium efficiency of rich lithium cathode sheet, and then improve coulombic efficiency first and the high rate performance of lithium rechargeable battery.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, described negative current collector can be porous current collector.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, the negative electrode active material in described negative electrode active material layer can be selected from graphite, silicon, SiO
x(0<x<2) one or more in.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, the described thickness containing lithium pulp layer can be 10 μm ~ 120 μm.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, the described one that can be selected from containing the coating method of lithium slurry on described negative current collector in silk screen printing, rotogravure application, extruding (Slot-die) coating, transfer coating.In one embodiment, when adopting silk screen printing, non-aqueous organic solvent can adopt high boiling non-aqueous organic solvent, prevents from thus containing lithium slurry by air oxygen detrition on printing screen plate, thus can provide excellent printing quality.The boiling point of described high boiling non-aqueous organic solvent can be greater than 90 DEG C, preferably can be greater than 100 DEG C.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, described dispersant can be non-ionic (polymeric surfactant), and described dispersant can be used for stable described containing lithium slurry.When adopting silk screen printing, described dispersant not only can be used for stable described to be fixed on the dot location on negative plate surface containing lithium slurry containing lithium slurry.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, the HLB value of described non-ionic (polymeric surfactant) can be 10 ~ 18.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, the weight average molecular weight of described non-ionic (polymeric surfactant) can be 800 ~ 1300000.If the weight average molecular weight of non-ionic (polymeric surfactant) is too low, then stable contain lithium slurry containing needing in lithium slurry could be formed compared with multi-dispersant, and lithium metal powder can closely wrap up by more dispersant, the capacity of lithium is hindered to play, reduce quantity and the electron conduction of lithium ion tunnel, and the weight average molecular weight of non-ionic (polymeric surfactant) is too low, then its strand is shorter, can not play sterically hindered effect well.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, described non-ionic (polymeric surfactant) can contain polar group, and described polar group can be selected from one or more in amino, hydroxyl, amide groups, ether, carboxyl and halogen.Described polar group is because of composition difference with positive charge or negative electrical charge, and when described polar group is with negative electrical charge, the lithium metal powder of meeting and surface band positive charge is linked together by electrostatic attraction effect; When described polar group is with positive charge, meeting can away from the lithium metal powder of surface band positive charge due to electrostatic repulsion, thus the strand of non-ionic (polymeric surfactant) can be formed sterically hindered between the particle of lithium metal powder, thus contribute to being formed stable containing lithium slurry.
One or more in the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, in the optional zoarium of the ring opening copolymer from polyalcohols, polyethers, Kynoar, polyacrylic acid and derivative thereof, PEO-PPO, cyclic imino ether of described non-ionic (polymeric surfactant), polyvinyl lactams, cellulose and its derivates.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, particularly, described non-ionic (polymeric surfactant) one or more in polyethylene glycol oxide (PEO), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), vinylpyrrolidone graft copolymer (AgrimerAL10) and hydroxypropyl methylcellulose (HPMC) optional.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, described conductive agent can be selected from one or more in material with carbon element, conducting polymer, metal and metal oxide, preferably can be material with carbon element.Described conductive agent can stop dispersant to wrap up lithium metal powder completely, thus the capacity being conducive to lithium plays.When conductive agent is material with carbon element, because the carbon atom of material with carbon element adopts SP2 hydridization, therefore surface is with negative electrical charge, is adsorbed on the surface of lithium metal powder by electrostatic attraction effect, thus forms conductive layer, avoids lithium metal powder to be wrapped up by dispersant completely; And the existence of material with carbon element also provides enough electron channels, add the probability that electrolyte contacts with lithium metal powder, thus the calandering steps in traditional rich lithium technique can be saved.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, described material with carbon element one or more in conductive carbon black SP, electrically conductive graphite KS-6, electrically conductive graphite SFG-6, Ketjen black EC300J, Ketjen black ECP, Ketjen black ECP-600JD, carbon nano-tube (CNT) and vapor-grown carbon fibers (VGCF), Graphene (Graphene) optional, preferably can be conductive carbon black SP.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, described conducting polymer one or more in polythiophene (PTH), polyaniline (PANI), polypyrrole (PPy), polyacetylene (PA), polyphenylacetylene (PPV) optional.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, described metal can be selected from one or more in Ag, Au, Ca, Cr, Ni, Mn, Sn, Zn.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, the optional autoxidation vanadium of described metal oxide (V
2o
5), tin oxide (SnO
2), one or more in zinc oxide (ZnO).
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, described lithium metal powder can be spherical, and the mean particle size D50 of described lithium metal powder can be 5 μm ~ 100 μm, preferably can be 20 μm ~ 50 μm.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, described non-aqueous organic solvent can be selected from one or more in aromatic hydrocarbon, alicyclic, halogenated hydrocarbons, ester class, ketone, preferably can be carbonic ester.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, described carbonic ester can be selected from one or more in ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and dibutyl carbonate (DBC).
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, the weight of described dispersant can be 0.2% ~ 5% of the described total weight containing lithium pulp layer.When the content of dispersant is less than 0.2%, it can not play dispersion and the stable effect containing lithium slurry, easily causes lithium metal powder containing floating in lithium slurry and causing containing the layering of lithium slurry; When the content of dispersant is greater than 5%, the conductivity of negative plate can be deteriorated, thus is unfavorable for that the capacity of lithium plays.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, the weight of described conductive agent can be 0.1% ~ 10% of the described total weight containing lithium pulp layer.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, the weight of described lithium metal powder can be 16% ~ 50% of the described total weight containing lithium pulp layer.When the content of lithium metal powder is less than 16%, the quantity not sufficient of the lithium metal that negative plate prints is to reach the effect of mending lithium, namely the effect of the consumption of the lithium made up in first charge-discharge process can not be played, and the manufacturing cost of lithium rechargeable battery can be increased, and cause the internal resistance of lithium rechargeable battery and the increase of polarization; When the content of lithium metal powder is greater than 50%, because the density of lithium metal is little, volume large, be therefore difficult to carry out the stirring containing lithium slurry.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, the weight of described non-aqueous organic solvent can be 40% ~ 70% of the described total weight containing lithium pulp layer.When the content of non-aqueous organic solvent is less than 30%, the viscosity containing lithium slurry is higher, and solid content is too high, causes and cannot stir; When the content of non-aqueous organic solvent is more than 80%, the viscosity containing lithium slurry is too low, easily causes leaking material, causes coating not easily to be carried out, or the lithium slurry that contains of coating easily flows in transfer process, causes the uniformity containing lithium pulp layer of formation poor.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, described containing lithium pulp layer also can comprise in non-lithium oxide powder one or more, described non-oxidate for lithium can be selected from SiO
2, HfO
2, SrTiO
3, SnO
2, CeO2, MgO, NiO, CaO, ZnO, ZrO
2, Y
2o
3, Al
2o
3, TiO
2in one or more, to improve the thixotropy containing lithium slurry, be conducive to the even coating containing lithium slurry.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, the weight of described non-lithium oxide powder can be 0.1% ~ 10% of the described total weight containing lithium pulp layer.
In the rich lithium cathode sheet of lithium rechargeable battery described according to a first aspect of the present invention, the electrolyte of described lithium rechargeable 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), dimethyl-tetrahydrofuran (2Me-THF), oxolane (THF), butylene (BC), 1, 2-dimethoxy-ethane (DME), dibutyl carbonate (DBC), carbonic acid first butyl ester (BMC), dipropyl carbonate (DPC), methyl esters (PA), ethyl acetate (MA), methyl formate (MF), one or more in methyl propionate (MP).
Secondly lithium rechargeable battery is according to a second aspect of the present invention described.
Lithium rechargeable battery according to a second aspect of the present invention, comprising: positive plate; Negative plate; Barrier film, between positive plate and negative plate; And electrolyte.Wherein, described negative plate is the rich lithium cathode sheet of lithium rechargeable battery according to a first aspect of the present invention.
Following explanation according to lithium rechargeable battery of the present invention and rich lithium cathode sheet thereof and embodiment and comparative example.
Embodiment 1
1. the preparation of the original negative pole piece of lithium rechargeable battery
By negative electrode active material graphite and SiO
x(0<x<2) (weight ratio 1:1, the gram volume of graphite is 340mAh/g, first coulombic efficiency is 91%, SiO to mixture
x(0<x<2) gram volume is 1135mAh/g, first coulombic efficiency is 58.4%), (specific area BET is 62m for bonding agent butadiene-styrene rubber, conductive agent conductive carbon black SP
2/ g) in mass ratio 92:3:5 mix with solvent N-methyl pyrilidone (NMP) and make cathode size, afterwards according to 121mg/1540mm
2coat weight cathode size is evenly coated on the tow sides of porous current collector Copper Foil, then cathode membrane is formed after drying at 85 DEG C, and the water content of cathode membrane is no more than 300ppm, then carry out colding pressing, trimming, cut-parts, itemize, welding negative lug, obtain the original negative pole piece that width is 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 is 14, and weight average molecular weight is 600000), (specific area BET is 62m to conductive agent conductive carbon black SP
2/ g), lithium metal powder (D50 is 40 μm), non-aqueous organic solvent propene carbonate (PC), the mixture (weight ratio is 3:2:3) of ethylene carbonate (EC) and diethyl carbonate (DEC) mixes by weight 0.6:0.4:30:69, obtain containing lithium slurry, afterwards by the surface being coated in the original negative pole piece of gained containing lithium slurry screen printing technique of gained, namely the rich lithium cathode sheet of lithium rechargeable battery is obtained after drying, wherein, formed containing lithium pulp layer after the drying containing lithium slurry, thickness containing lithium pulp layer is 60 μm, be spot distribution containing lithium pulp layer and spacing is between points 100 μm.
3. the preparation of the positive plate of lithium rechargeable battery
By positive active material cobalt acid lithium (LiCoO
2), (specific area BET is 62m for binding agent Kynoar (PVDF), conductive agent conductive carbon black SP
2/ g) in mass ratio 97:1.5:1.5 be dissolved in solvent N-methyl pyrilidone (NMP), stir and make anode sizing agent, then anode sizing agent is uniformly coated on positive and negative two surfaces of plus plate current-collecting body aluminium foil, 118 μm of thick positive pole diaphragms are obtained after drying at 85 DEG C afterwards, afterwards through colding pressing, cut into slices, itemize, welding positive pole ear, obtain the positive plate of lithium rechargeable battery.
4. the preparation of the electrolyte of lithium rechargeable battery
By lithium salts LiPF
6with the electrolyte of non-aqueous organic solvent (ethylene carbonate (EC): diethyl carbonate (DEC): methyl ethyl carbonate (EMC): vinylene carbonate (VC)=8:85:5:2, the mass ratio) solution that 8:92 is formulated in mass ratio as lithium rechargeable battery.
5. the preparation of lithium rechargeable battery
After positive plate, barrier film (PE film) and rich lithium cathode sheet being reeled, obtain naked battery core, afterwards through encapsulating, injecting electrolyte, changing into, bleed shaping, obtain lithium rechargeable battery.
Embodiment 2
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, non-aqueous organic solvent is the mixture (weight ratio is 3:2) of propene carbonate (PC) and dimethyl carbonate (DMC), dispersant: conductive agent: lithium metal powder: the weight ratio of non-aqueous organic solvent is 0.2:0.8:30:69.
Embodiment 3
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, non-aqueous organic solvent is the mixture (weight ratio is 1:3) of propene carbonate (PC) and ethylene carbonate (EC), dispersant: conductive agent: lithium metal powder: the weight ratio of non-aqueous organic solvent is 0.6:0.1:30:69.3.
Embodiment 4
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, non-aqueous organic solvent is the mixture (weight ratio is 2:3) of diethyl carbonate (DEC) and propene carbonate (PC), dispersant: conductive agent: lithium metal powder: the weight ratio of non-aqueous organic solvent is 0.4:0.6:30:69.
Embodiment 5
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, dispersant is polyvinyl alcohol (PVA), HLB value is 12, weight average molecular weight is 16000, and non-aqueous organic solvent is propene carbonate (PC).
Embodiment 6
Method according to embodiment 5 prepares lithium rechargeable battery, just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, dispersant is polyvinylpyrrolidone (PVP), and HLB value is 17, and weight average molecular weight is 1300000.
Embodiment 7
Method according to embodiment 6 prepares lithium rechargeable battery, just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, conductive carbon is carbon nano-tube CNT, and average diameter is 11nm, average length is 10 μm, and specific area BET is 240m
2/ g.
Embodiment 8
Method according to embodiment 6 prepares lithium rechargeable battery, and just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, conductive carbon is electrically conductive graphite KS-6, D50 is 5 μm, and specific area BET is 20m
2/ g.
Embodiment 9
Method according to embodiment 7 prepares lithium rechargeable battery, and just in the preparation (i.e. step (1)) of the original negative pole piece of lithium rechargeable battery, negative electrode active material is graphite.
Embodiment 10
Method according to embodiment 7 prepares lithium rechargeable battery, just in the preparation (i.e. step (1)) of the original negative pole piece of lithium rechargeable battery, negative electrode active material is the mixture of graphite and silicon, the weight ratio of the two is 3:1, wherein, the gram volume of silicon is 3800mAh/g, first coulombic efficiency is 62%.
Embodiment 11
Method according to embodiment 7 prepares lithium rechargeable battery, just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, dispersant is vinylpyrrolidone graft copolymer (AgrimerAL10, HLB value is 18, weight average molecular weight is 1000000), non-aqueous organic solvent is the mixture (weight ratio is 1:3) of propene carbonate (PC) and ethylene carbonate (EC), dispersant: conductive agent: lithium metal powder: the weight ratio of non-aqueous organic solvent is 5:5:50:40.
Embodiment 12
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, dispersant is hydroxypropyl methylcellulose (HPMC, HLB value is 10, weight average molecular weight is 800), non-aqueous organic solvent is the mixture (weight ratio is 4:2:3) of dimethyl carbonate (DMC), ethylene carbonate (EC) and propene carbonate (PC), dispersant: conductive agent: lithium metal powder: the weight ratio of non-aqueous organic solvent is 5:10:16:69.
Embodiment 13
Method according to embodiment 4 prepares lithium rechargeable battery, and just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, also contain non-lithium oxide powder containing in lithium slurry, non-lithium oxide powder is Al
2o
3(particle diameter is 30nm, and specific area is 150m
2/ g), dispersant: conductive agent: lithium metal powder: non-lithium oxide powder: the weight ratio of non-aqueous organic solvent is 0.4:0.6:30:1:68.
Embodiment 14
Method according to embodiment 13 prepares lithium rechargeable battery, and just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, also contain non-lithium oxide powder containing in lithium slurry, non-lithium oxide powder is TiO
2, particle diameter is 30nm, and specific area is 150m
2/ g.
Embodiment 15
Method according to embodiment 13 prepares lithium rechargeable battery, and just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, also contain non-lithium oxide powder containing in lithium slurry, non-lithium oxide powder is SiO
2, particle diameter is 50nm, and specific area is 120m
2/ g.
Embodiment 16
Method according to embodiment 15 prepares lithium rechargeable battery, just dispersant in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery: conductive agent: lithium metal powder: non-lithium oxide powder: the weight ratio of non-aqueous organic solvent is 0.4:0.6:30:2:67.
Embodiment 17
Method according to embodiment 15 prepares lithium rechargeable battery, just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, dispersant: conductive agent: lithium metal powder: non-lithium oxide powder: the weight ratio of non-aqueous organic solvent is 0.4:0.6:30:6:63.
Embodiment 18
Method according to embodiment 15 prepares lithium rechargeable battery, just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, dispersant: conductive agent: lithium metal powder: non-lithium oxide powder: the weight ratio of non-aqueous organic solvent is 0.4:0.6:30:10:59.
Embodiment 19
Method according to embodiment 15 prepares lithium rechargeable battery, just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, dispersant: conductive agent: lithium metal powder: non-lithium oxide powder: the weight ratio of non-aqueous organic solvent is 0.4:0.6:30:0.1:68.9.
Comparative example 1
Method according to embodiment 1 prepares lithium rechargeable battery, just in the preparation (i.e. step (2)) of the rich lithium cathode sheet of lithium rechargeable battery, do not add conductive agent, dispersant: lithium metal powder: the weight ratio of non-aqueous organic solvent is 0.6:30:69.4.
Test process according to lithium rechargeable battery of the present invention and rich lithium cathode sheet thereof and test result are finally described.
1. containing the weight variation coefficient of lithium pulp layer
Adopt precision be the weight (being designated as A) of the electronic balance weighing original negative pole piece of 0.001g, the coating of original negative pole piece one side containing the weight (being designated as B) after lithium pulp layer, original negative pole piece dual coating containing the weight (being designated as C) after lithium pulp layer, the then clean coated weight WS=B-A of original negative pole piece one side, the two-sided clean coated weight WD=C-A of original negative pole piece.
In formula (1) ~ (4), n is sampling number of samples, herein n=50.
Weight variation coefficient (%)=one side standard deviation/one side average × 100% of one side coating;
Weight variation coefficient (%)=two-sided standard deviation/two-sided average × 100% of dual coating.
2. the lithium of analysing of rich lithium cathode sheet is tested
Observe rich lithium cathode sheet surface and analyse the serious and uniformity coefficient of lithium, wherein analyse lithium degree and be divided into and slightly analyse lithium, analyse lithium and seriously analyse lithium.Slightly analyse lithium and represent that the lithium region of analysing of membrane surface is less than 20%, analyse lithium and represent that the lithium region of analysing of membrane surface is 20% ~ 70%, seriously analyse lithium and represent that the lithium region of analysing of membrane surface is greater than 70%.
3. the bending dry linting test of rich lithium cathode sheet
By rich lithium cathode sheet doubling, observe and whether come off from porous current collector at the diaphragm at doubling folding line place.Wherein "None" represents that the area that the diaphragm at doubling folding line place comes off from porous current collector is less than 5%, " slightly " represents that the diaphragm at doubling folding line place is 5% ~ 50% from the area that porous current collector comes off, and " seriously " represents that the area that the diaphragm at doubling folding line place comes off from porous current collector is greater than 50%.
4. the volume test of lithium rechargeable battery
At 25 DEG C, first with the constant current of 0.02C multiplying power, 3.9V is charged to lithium rechargeable battery, this charging capacity is designated as ICC0, with the constant current of 0.5C multiplying power, 4.4V is charged to lithium rechargeable battery subsequently, this charging capacity is designated as AGC0, then be discharged to 3.0V with the constant current of 0.7C multiplying power to lithium rechargeable battery, this discharge capacity is designated as D0.
Coulombic efficiency first (the %)=D0/ (ICC0+AGC0) × 100% of lithium rechargeable battery.
5. internal resistance (IMP) test of lithium rechargeable battery
The impedance of the lithium rechargeable battery on ac impedance measurement instrument after test capacity test, the frequency used during test is 1000Hz.
6. the high rate performance test of lithium rechargeable battery
Lithium rechargeable battery after volume test is completely filled, discharges with the constant current of 0.2C and 2C multiplying power respectively afterwards, record respective discharge capacity D1 and D2.
2C/0.2C high rate performance (%)=D2/D1 × 100% of lithium rechargeable battery.
7. self discharge (K value) test of lithium rechargeable battery
Be transferred to by lithium rechargeable battery after volume test in the oven of 45 DEG C and toast 24h, taken out by lithium rechargeable battery afterwards and at room temperature leave standstill 24h, the open circuit voltage of test lithium rechargeable battery is designated as OCV1; Again lithium rechargeable battery is at room temperature left standstill 72h, the open circuit voltage of test lithium rechargeable battery is designated as OCV2.
Voltage drop (i.e. K the value)=OCV1-OCV2 of lithium rechargeable battery.
Table 1 provides 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 is analyzed.
As can be seen from the contrast of embodiment 1-19 and comparative example 1, use the internal resistance (IMP) of the lithium rechargeable battery of rich lithium cathode sheet of the present invention and self discharge (K value) not to be significantly increased, and the coulombic efficiency first of lithium rechargeable battery and high rate performance are obviously promoted.This is because the non-aqueous organic solvent contained in lithium pulp layer of the present invention can by swelling for the bonding agent on negative plate surface, improve the voidage on negative plate surface, make there is more lithium ion tunnel between lithium metal powder, electrolyte, negative plate three, thus promote the benefit lithium efficiency of negative plate, and then improve coulombic efficiency first and the high rate performance of lithium rechargeable battery.
It can also be seen that from the contrast of embodiment 1 and embodiment 3, along with the weight percentage of conductive agent increases, the coulombic efficiency first of lithium rechargeable battery and high rate performance all increase.
As can be seen from the contrast of embodiment 1 and embodiment 5-6, adopt PEO as the coulombic efficiency first of the lithium rechargeable battery of dispersant and high rate performance than adopt PVA and PVP as the coulombic efficiency first of the lithium rechargeable battery of dispersant and high rate performance all good.This is because PEO to have the ability of the stronger lithium salts that dissociates relative to PVA and PVP, and stablizes lithium; In the charge and discharge process of lithium rechargeable battery, oxygen atom in lithium ion and PEO is constantly carried out complexing by coordination and is dissociated, thus be conducive to the fast transferring of lithium ion at inside battery, and then the coulombic efficiency first of PEO and high rate performance comparatively PVA go with PVP.
As can be seen from the contrast of embodiment 6-8, along with the specific area of conductive agent increases, the coulombic efficiency first of lithium rechargeable battery reduces, but the high rate performance of lithium rechargeable battery increases.This is that conductive agent particle has the surface contact of more probability and lithium metal powder, and provides more electron channel, thus increases the migration rate of electronics, and then improves the high rate performance of lithium rechargeable battery due to when the specific area of conductive agent increases; But after the specific area of conductive agent increases, in formation process, conductive agent particle surface can form more SEI film, and then consumes more lithium, therefore causes the coulombic efficiency first of lithium rechargeable battery to reduce.
As can be seen from the contrast of embodiment 4 and embodiment 13-19, thixotropy containing lithium slurry can be improved to containing adding non-oxidate for lithium in lithium slurry, improve containing the dispersion effect of each solid constituent in non-aqueous organic solvent in lithium slurry, and then the uniformity improved containing the coating of lithium slurry, be embodied in the reduction of the weight variation coefficient containing lithium pulp layer, namely, in coating procedure, the weight consistency containing lithium pulp layer improves.
It can also be seen that from the contrast of embodiment 13-15, adopt TiO
2as coulombic efficiency first and the high rate performance ratio employing Al of the lithium rechargeable battery of non-oxidate for lithium
2o
3and SiO
2all to get well as the coulombic efficiency first of the lithium rechargeable battery of non-oxidate for lithium and high rate performance.This is due to TiO
2removal lithium embedded invertibity better, structural stability is high, can provide more lithium ion tunnel and larger embedding lithium capacity.
It can also be seen that from the contrast of embodiment 15-19, along with SiO
2weight percentage increase, the high rate performance of lithium rechargeable battery increases, and the internal resistance of lithium rechargeable battery (IMP) reduces.This is the SiO owing to containing in lithium pulp layer
2the increase of weight percentage can improve thixotropy containing lithium slurry and impressionability, make containing lithium slurry dispersedly evenly, thus make film evenly, and then improve containing the weight consistency of lithium pulp layer, the internal resistance (IMP) of final lithium rechargeable battery reduces; The uniformity increase of film can reduce the migration resistance of lithium ion, and then makes lithium rechargeable battery have good high rate performance.
Claims (10)
1. a rich lithium cathode sheet for lithium rechargeable battery, comprising:
Negative current collector; And
Negative electrode active material layer, is coated in the surface of negative current collector containing negative electrode active material;
It is characterized in that,
Described negative electrode active material layer is away from the surface of negative current collector being coated with containing lithium pulp layer;
The described lithium pulp layer that contains comprises dispersant, conductive agent, lithium metal powder and non-aqueous organic solvent, and wherein the electrolyte of non-aqueous organic solvent and lithium rechargeable battery dissolves each other.
2. the rich lithium cathode sheet of lithium rechargeable battery according to claim 1, it is characterized in that, described dispersant is non-ionic (polymeric surfactant), described non-ionic (polymeric surfactant) contains polar group, and described polar group is selected from one or more in amino, hydroxyl, amide groups, ether, carboxyl and halogen.
3. the rich lithium cathode sheet of lithium rechargeable battery according to claim 2, it is characterized in that, described non-ionic (polymeric surfactant) is selected from one or more in polyalcohols, polyethers, Kynoar, polyacrylic acid and derivative thereof, PEO-PPO, fit, the polyvinyl lactams of ring opening copolymer of cyclic imino ether and cellulose and its derivates.
4. the rich lithium cathode sheet of lithium rechargeable battery according to claim 1, is characterized in that, described conductive agent is selected from one or more in material with carbon element, conducting polymer, metal and metal oxide, is preferably material with carbon element.
5. the rich lithium cathode sheet of lithium rechargeable battery according to claim 1, is characterized in that, described lithium metal powder is spherical, and the average grain diameter D50 of the particle of described lithium metal powder is 5 μm ~ 100 μm, is preferably 20 μm ~ 50 μm.
6. the rich lithium cathode sheet of lithium rechargeable battery according to claim 1, is characterized in that, described non-aqueous organic solvent is selected from one or more in aromatic hydrocarbon, alicyclic, halogenated hydrocarbons, ester class, ketone, is preferably carbonic ester.
7. the rich lithium cathode sheet of lithium rechargeable battery according to claim 1, is characterized in that,
The weight of described dispersant is 0.2% ~ 5% of the described total weight containing lithium pulp layer;
The weight of described conductive agent is 0.1% ~ 10% of the described total weight containing lithium pulp layer;
The weight of described lithium metal powder is 16% ~ 50% of the described total weight containing lithium pulp layer;
The weight of described non-aqueous organic solvent is 40% ~ 70% of the described total weight containing lithium pulp layer.
8. the rich lithium cathode sheet of lithium rechargeable battery according to claim 1, is characterized in that, the described lithium pulp layer that contains also comprises non-lithium oxide powder, and described non-oxidate for lithium is selected from SiO
2, HfO
2, SrTiO
3, SnO
2, CeO
2, MgO, NiO, CaO, ZnO, ZrO
2, Y
2o
3, Al
2o
3, TiO
2in one or more, the weight of described non-lithium oxide powder is 0.1% ~ 10% of the described total weight containing lithium pulp layer.
9. the rich lithium cathode sheet of lithium rechargeable battery according to claim 1, it is characterized in that, the electrolyte of described lithium rechargeable battery is 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), dimethyl-tetrahydrofuran (2Me-THF), oxolane (THF), butylene (BC), 1, 2-dimethoxy-ethane (DME), dibutyl carbonate (DBC), carbonic acid first butyl ester (BMC), dipropyl carbonate (DPC), methyl esters (PA), ethyl acetate (MA), methyl formate (MF), one or more in methyl propionate (MP).
10. a lithium rechargeable battery, comprising:
Positive plate;
Negative plate;
Barrier film, between positive plate and negative plate; And
Electrolyte;
It is characterized in that, the rich lithium cathode sheet that described negative plate is the lithium rechargeable battery according to any one of claim 1-9.
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