CN102201565B - High-capacity metal lithium powder composite cathode and preparation method thereof, and multi-layer composite electrode - Google Patents
High-capacity metal lithium powder composite cathode and preparation method thereof, and multi-layer composite electrode Download PDFInfo
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- CN102201565B CN102201565B CN2011100935373A CN201110093537A CN102201565B CN 102201565 B CN102201565 B CN 102201565B CN 2011100935373 A CN2011100935373 A CN 2011100935373A CN 201110093537 A CN201110093537 A CN 201110093537A CN 102201565 B CN102201565 B CN 102201565B
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Abstract
The invention discloses a high-capacity metal lithium powder composite cathode and a preparation method thereof and a multi-layer composite electrode. The high-capacity metal lithium powder composite cathode comprises the following components in part by weight: 1 to 80 parts of metal lithium powder, 10 to 90 parts of cathode powder, 1 to 10 parts of conductive agent, 1 to 4.5 parts of adhesive and 0 to 0.5 part of surfactant. By compounding the metal lithium powder with materials such as graphite, soft carbon, hard carbon, tin and oxides thereof, silicon and oxides thereof and the like, mass ratio capacity and volume ratio capacity of a cathode material are improved, using amount of active substances is reduced, and the battery specific capacity is improved; the specific capacity of the cathode can be adjusted by adjusting the rate of metal lithium to the graphite; short circuit in a battery caused by piercing of a diaphragm through metal dendritic crystal growth can be effectively prevented through the separation of an insulating protective layer, so that the safety performance of the battery is improved; and the metal lithium powder is counteracted with irreversible capacity loss of the cathode, and primary Kulun efficiencies of the graphite, the hard carbon, the soft carbon, the tin, the silicon and other cathode materials are improved.
Description
Technical field
The present invention relates to field of electrochemical power source, relate in particular to composite negative pole of the materials such as a kind of lithium metal powder of high power capacity and graphite, hard carbon, silicon, tin and preparation method thereof.
Background technology
Lithium ion battery has been widely used in fields such as mobile phone, notebook computer, portable type electronic products, and will have wide practical use in fields such as electric tool, electric motor cars.Electric tool and electric automobile field require motive-power battery to have higher energy density, lower cost and the fail safe of Geng Gao.
How to improve the charge-discharge performance of battery, the satisfying the market requirement is the hot issue of pendulum in face of battery operated person.For this reason, battery operated person has carried out continuous exploration at aspects such as the structural design of battery, both positive and negative polarity composition, battery production technologies.Wherein the combination property of battery in the chemical property appreciable impact of both positive and negative polarity.Present traditional lithium ion battery be mainly with carbon materials as negative pole, the materials such as cobalt acid lithium, LiFePO4 are as positive pole, its performance more and more can not satisfy the requirement of above-mentioned development.Therefore, the research and development of the positive and negative pole material of high power capacity or high-capacity battery system such as lithium-sulfur cell etc. have become the focus that people pay close attention to.Wherein conventional graphite cathode energy density is low is only 372mAh/g, is one of raising key factor of restriction lithium secondary battery energy density.In addition, the coupling that traditional graphite cathode material and lithium-sulfur cell high power capacity positive pole can not be good has affected the performance of positive electrode capacity.Therefore, improving capacity of negative plates is the effective way that improves lithium ion battery energy density or performance lithium-sulfur cell capacity.
Lithium metal is metal Atom amount minimum (6.94), the richest metal of standard electrode potential (3.045V), its theoretical specific capacity is up to 3860mAh/g, it is the very high negative material of a kind of energy density, but owing to very easily forming dendrite in the relatively poor and cyclic process of its chemical stability, easily pierce through barrier film, cause the cell safety problem, can't satisfy the actual needs as cell negative electrode material.Normally by being added with organic additive such as VC etc. or inorganic additive such as CO in electrolyte
2, Al
2O
3Deng the problem of improving dendrite (referring to Kanamura K, Okagawa T, Takehara z.J.Power Sources, 1995,57:119-123) or coat cycle performance and the security performance that modification improves lithium anode on its surface.
Some studies show that, and after the lithium anode powdered (can be referring to Kwon C W, Cheon S E, Song J M.et.al, J.Power Sources, 2001,93:145-150; And Park M S, Yoon WY.J.Power Sources, 2003,114:237-243), the increase of negative pole interface impedance is significantly alleviated, and illustrates that cycle performance and the security performance of lithium metal powder negative pole is better.Yet powdered has only improved the specific discharge capacity of lithium anode, and its volume and capacity ratio is but very low, secondly because the particle Contact is loose, contact resistance is larger, and in the repeated charge process, the metallic lithium powder particle is grown up gradually, has lost the advantage of powdered.The people such as the Sun Hao of Tsing-Hua University disclosed " lithium ion battery with the preparation method of hard carbon lithium metal composite negative pole material (application number: 200610089725.8) ".But this patent is that the lithium powder with minute quantity is doped in hard carbon cathode material or with the lithium paper tinsel and is pressed onto on the hard carbon cathode sheet, with the compensation irreversible capacity loss, improves battery efficient first.
Different from a kind of high power capacity composite negative pole and technology of preparing thereof of one or more preparations wherein such as lithium metal powder and graphite, soft carbon, hard carbon, silicon, tin of adopting disclosed by the invention.Metallic lithium powder composite negative pole technology disclosed by the invention be with metallic lithium powder as negative electrode active material, performance capacity in cyclic process.by and graphite, soft carbon, hard carbon, silicon, the compound of the materials such as tin can not only effectively be improved graphite, soft carbon, hard carbon, silicon, the specific energy of tin negative pole material improves the volumetric specific energy of lithium metal powder simultaneously, thereby obtain high-quality ratio and volumetric specific energy negative pole, and, the lithium metal powder can effectively compensate the carbon negative pole, the irreversible capacity loss of the materials such as silicium cathode in the first charge-discharge process, improve material efficient first, in addition, can prevent effectively that by the multi-layered electrode technology of preparing Li dendrite that in the repeated charge process, lithium metal powder forms from piercing through the problem that barrier film causes battery short circuit.Negative pole of the present invention is not only applicable to traditional lithium ion battery field, improves battery capacity and reduces the negative material consumption, and can be used as the negative pole of high power capacity lithium-sulfur cell of future generation.
Summary of the invention
The invention provides composite negative pole of a kind of high-energy-density that is applicable to lithium ion battery, lithium-sulfur cell and preparation method thereof.By lithium metal powder and graphite, soft carbon, hard carbon, silicon and the materials such as oxide, tin and oxide thereof thereof are mixed with composite negative pole, thereby improve the specific capacity of negative pole.And can regulate the specific capacity of negative pole to adapt to anodal needs by the ratio of adjusting the negative materials such as lithium metal powder and carbon, tin, silicon within the specific limits.By applying insulating protective layer at electrode surface, prevent that further Li dendrite from piercing through barrier film and causing internal short-circuit in addition, improve the security performance of battery.The present invention also provides the application conditions of metallic lithium powder composite negative pole, because the growth to Li dendrite of pole piece assembling pressure and inner pressure of battery has a great impact, by increasing electrode assembling pressure and increasing the growth that inner pressure of battery can effectively suppress Li dendrite, therefore utilize the pressure traditional lithium ion battery relative to inner pressure of battery of metallic lithium powder composite negative pole assembled battery larger.
A kind of high-capacity metal lithium powder composite cathode, its weight portion consists of:
1～80 part of metallic lithium powder;
10～90 parts, negative pole powder;
1～10 part of conductive agent;
1～4.5 part of binding agent;
0～0.5 part, surfactant.
Wherein surfactant is selectable components, certainly as preferred, and interpolation surfactant that can be appropriate.For example dosage of surfactant is 0.2～0.5 weight portion, and to improve diffusivity, described surfactant can adopt polyvinylpyrrolidone (PVP) etc.
As preferably, described high-capacity metal lithium powder composite cathode, its weight portion consists of:
10～50 parts of metallic lithium powders;
40～90 parts, negative pole powder;
3～8 parts of conductive agents;
1～4.5 part of binding agent;
0.2～0.5 part, surfactant.
As further preferred, described high-capacity metal lithium powder composite cathode, its weight portion consists of:
10～30 parts of metallic lithium powders;
60～80 parts, negative pole powder;
2～5 parts of conductive agents;
1～4.5 part of binding agent;
0.2～0.5 part, surfactant.
Described negative pole powder is one or more in the oxide of oxide, silicon, silicon of graphite, soft carbon, hard carbon, tin, tin, and is Powdered.
Described conductive agent is one or more in acetylene black, electrically conductive graphite, carbon nano-tube, carbon fiber.
Described lithium metal powder can be the metallic lithium powder that commercially available surface coats stabilized zone, the lithium metal powder that perhaps prepares by CVD (Chemical Vapor Deposition) method, and its grain size scope is 10 nanometers～100 micron.The theoretical specific capacity of metallic lithium powder generally is decided to be 3860mAh/g by empirical value.Lithium metal powder not only can improve negative pole energy density and also can the balancing battery cyclic process in irreversible capacity loss, improve the enclosed pasture efficient of the negative poles such as Si.
Described binding agent is one or more in Kynoar (PVDF), polytetrafluoroethylene (PTFE), vinylacetate (EVA).
To use with the form of glue in being dispersed in the solvent of volatilizable type at the binding agent described in actual fabrication process, one or more in the solvent of volatilizable type such as toluene, hexane, heptane, dimethylbenzene, acetone; Binding agent and solvent can also adopt other general kinds, but guarantee that at least binding agent and solvent all do not react with metallic lithium powder.
Need the oven dry volatilization in subsequent process due to solvent, generally product do not had substantial effect, therefore the not strict restriction of the consumption of solvent, but in order to make good mixing and the dispersion of binding agent and other raw materials energy, weight of solvent can be generally 5～100 times of weight of binder.
The present invention also provides a kind of preparation method of described high-capacity metal lithium powder composite cathode, comprise: metallic lithium powder, negative pole powder and conductive agent are carried out mix and blend under inert atmosphere, obtain finely dispersed mixture, this mixture is joined mix and blend in glue, obtains slurry after being uniformly dispersed, and the slurry drying obtains described high-capacity metal lithium powder composite cathode.
Described glue is by described binding agent and solvent composition, described solvent can be toluene, hexane, heptane, dimethylbenzene or acetone etc., and described binding agent is Kynoar (PVDF), polytetrafluoroethylene (PTFE) or vinylacetate (EVA).Weight of solvent can be generally 5～100 times of weight of binder.
Due in the preparation process of battery, negative pole is to load on collector foil surface or substrate surface, therefore during practical operation, can slurry be applied to collection liquid surface with conductive adhesive layer by methods such as transfer coated or sprayings, drying, obtain described high-capacity metal lithium powder composite cathode after rolling.
The temperature range of described oven dry is 90～160 ℃, also can adopt with this understanding vacuum drying to promote the volatilization of solvent.
As preferably, when preparation mixture and slurry, all carry out under the inert atmosphere protections such as argon gas, mix and blend used adopts mechanical mixture.
The present invention also provides a kind of multi-layer composite electrode, by forming as lower floor's structure of distributing successively:
(a) collector;
(b) conductive adhesive layer;
(c) described high-capacity metal lithium powder composite cathode;
(d) hot pressing graphite linings;
(e) insulating protective layer that is formed by metal oxide;
Described collector can adopt prior art, such as being the materials such as electrolytic copper foil, rolled copper foil, copper mesh, carbon paper tinsel.
Described conductive adhesive layer can adopt the commercially available conducting resinl of Henkel Corp., or the conducting resinl that adopts following weight portion to form:
(A) glue is 40 parts;
(B) electrocondution slurry is 60 parts.
The weight portion of wherein said (A) glue consists of:
As 60～83 parts of the Sodium Polyacrylates (PAA) of binding agent;
As 16～40 parts, the water of solvent;
Ca (OH)
25 parts;
The weight portion of described (B) electrocondution slurry consists of:
As 5～55 parts of the acetylene blacks (SP) of conductive agent;
As 45～94 parts, the water of solvent.
Each component and also can adopt other schemes of the prior art with magnitude relation in conducting resinl.
The present invention also provides a kind of preparation method of described multi-layer composite electrode, comprises at first and is covering conductive adhesive layer at collection liquid surface, then successively formation high-capacity metal lithium powder composite cathode, hot pressing graphite linings and insulating protective layer.
Can adopt reticulate pattern roll printing brush or gravure process that conducting resinl is coated in collection liquid surface during the preparation conductive adhesive layer, 120 ℃ of oven dry make the collector with conductive adhesive layer.
Can by the ratio of raw material, change the specific capacity of negative pole to adapt to anodal needs in described high-capacity metal lithium powder composite cathode.
For example when consisting of metallic lithium powder 10 weight portions, negative pole powder 80 weight portions, conductive agent 5 weight portions, weight of binder part, the capacity of negative plates that obtains is about 683mAh/g.
If form when becoming metallic lithium powder 20 weight portions, negative pole powder 75 weight portions, conductive agent 2 weight portions, binding agent 3 weight portion, the capacity of negative plates that obtains is 1051mAh/g approximately.
When preparing described hot pressing graphite linings, graphite granule, conductive agent are mixed with PVDF emulsion or PTFE emulsion as binding agent, stirring is coated in plastics foil surface, and oven dry obtains graphite linings.The graphite linings that obtains is hot-pressed onto (the plastics foil is peeled off removal after hot pressing) on described high-capacity metal lithium powder composite cathode, and hot pressing temperature is 160 ℃.
Conductive agent in the hot pressing graphite linings is one or more in acetylene black, electrically conductive graphite, carbon nano-tube, carbon fiber.The weight ratio of graphite granule and conductive agent is 10～30: 1.
Described PVDF emulsion can adopt the commercially available prod, for example take acetone as dispersant, in emulsion, the mass percentage content of PVDF is 1～10%, and same described PTFE emulsion also can adopt the commercially available prod, for example take water as dispersant, in emulsion, the mass percentage content of PTFE is 1～10%.
When preparing described hot pressing graphite linings, because dispersant in emulsion can be adjusted in a big way, therefore the not strict restriction of the weight ratio of graphite granule and binding agent, in general graphite granule and emulsion, the weight ratio of PVDF or PTFE can be 1: 0.03～0.3.
The thickness range of described insulating protective layer (being protective oxide film) is at 0.1-20 μ m, and its raw material can be Al
2O
3, ZrO
2, TiO
2Or the metal oxide such as MgO.
Preparation joins oxide during insulating protective layer and is applied to the graphite linings surface in glue after dispersed with stirring, oven dry (90～140 ℃ of temperature) desolventizing at last.
Insulating protective layer is selected oxide ceramic material on raw material, form loose structure on microcosmic.Insulating protective layer can be that to be coated with and to cover on the graphite linings surface can be also to be coated on barrier film.Be coated in when using on barrier film, covering in the lump on the graphite linings surface together with barrier film, and insulating protective layer be adjacent with the graphite linings surface.
The glue that the glue that adopts during the preparation insulating protective layer adopts in the time of can adopting the described high-capacity metal lithium powder composite cathode of preparation contains the acetone of Kynoar (PVDF) etc. such as employing.
During the preparation insulating protective layer, because solvent in glue can be adjusted in a big way, so the not strict restriction of the weight ratio of metal oxide and glue, in common metal oxide and glue, the weight ratio of solute can be 1: 0.03～0.3.
As preferably, adopt Al
2O
3For raw material prepares insulating protective layer, Al
2O
3Can with electrolyte in the reactions such as PC, EC, be conducive at the effective passivating film of lithium metal powder Surface Creation, suppress the growth of Li dendrite.
The assembling pressure of the multi-layer composite electrode described in the present invention and the inner pressure of battery that uses this multi-layer composite electrode to prepare are higher, can suppress the growth of lithium metal dendrite.
Each layer structure in described multi-layer composite electrode, if there is no specified otherwise, the not strict restriction of its thickness can be according to prior art or actual demand design.
The present invention improves specific discharge capacity and the volume and capacity ratio of negative material by Material claddings such as lithium metal powder and graphite, soft carbon, hard carbon, tin and oxide, silicon and oxides thereof, reduce amount of active mass and improve the battery specific capacity; The specific capacity that can regulate negative pole by the ratio of adjusting lithium metal and graphite; Obstruct by insulating protective layer can prevent effectively that the metallic dendrite growth from piercing through barrier film and causing the battery internal short-circuit, improves the security performance of battery; Lithium metal powder is offset negative pole at irreversible capacity loss, has improved the efficient of enclosed pasture first of the negative materials such as graphite, hard carbon, soft carbon, tin, silicon.
Description of drawings
Fig. 1 is the structural representation of multi-layer composite electrode of the present invention.
Embodiment
Embodiment 1
the preparation of high-capacity metal lithium powder composite cathode: under the argon gas atmosphere protection, 30 grams are mixed and made into glue as the toluene of solvent and 4.5 grams as the Kynoar (PVDF) of binding agent, with 20 gram lithium metal powders, 40 grams are as the graphite of negative pole powder, 0.5 gram surfactant (polyvinylpyrrolidone (PVP)), 5 grams add in glue as the acetylene black of conductive agent, be sprayed into the collection liquid surface with conductive adhesive layer after stirring, (namely be sprayed into the conductive adhesive layer surface, wherein the collector with conductive adhesive layer can utilize prior art preparation or commercial), dry under 120 ℃ of conditions and roll, namely complete the preparation of high-capacity metal lithium powder composite cathode on the conductive adhesive layer surface, the specific capacity of the high-capacity metal lithium powder composite cathode for preparing after testing can reach 1315mAh/g.
Embodiment 2
Referring to Fig. 1, a kind of multi-layer composite electrode is made of the collector 1, conductive adhesive layer 2, high-capacity metal lithium powder composite cathode 3, hot pressing graphite linings 4, insulating protective layer 5 and the barrier film 6 that distribute successively.Its preparation method is as follows:
Preparation with the collector of conductive adhesive layer: get thickness and be the Copper Foil of 10 μ m as collector, with 30 gram Sodium Polyacrylates (PAA), 8 gram water and 2 gram Ca (OH)
2Mix and make 40 gram glue A, with 5 gram acetylene blacks (SP), 55 gram water mix makes 60 gram electrocondution slurries, gets 40 and restrains the glue A get ready and add to mix in 60 gram electrocondution slurries and obtain conducting resinl.
Adopt gravure process that conducting resinl is coated in the Copper Foil collection liquid surface, 120 ℃ of oven dry obtain the collector with conductive adhesive layer, reel stand-by.
The preparation of high-capacity metal lithium powder composite cathode:
under the argon gas atmosphere protection, 30 grams are mixed and made into glue as the toluene of solvent and 4.5 grams as the Kynoar (PVDF) of binding agent, with 20 gram lithium metal powders, 40 grams are as the graphite of negative pole powder, 0.5 gram surfactant (polyvinylpyrrolidone (PVP)), 5 grams add in glue as the acetylene black of conductive agent, be sprayed into the conductive adhesive layer surface after stirring, dry under 120 ℃ of conditions and roll, namely complete the preparation of high-capacity metal lithium powder composite cathode on the conductive adhesive layer surface, the specific capacity of this high-capacity metal lithium powder composite cathode can reach 1315mAh/g.
The preparation of hot pressing graphite linings: 47.5 gram graphite granules are mixed as the PVDF emulsion of binding agent with acetylene black and 50 grams of 2.5 grams as conductive agent, stirring, it is surperficial to be coated in the plastics foil, oven dry obtains graphite linings, the graphite linings that obtains is hot-pressed onto the surface of high-capacity metal lithium powder composite cathode, hot pressing temperature is 160 ℃, then peels off the plastics foil.Wherein the PVDF emulsion is take acetone as dispersant, and in emulsion, the mass percentage content of PVDF is 5%.High-capacity metal lithium powder composite cathode and hot pressing graphite linings are calculated as a whole, and its specific capacity is about 915mAh/g.
The preparation of insulating protective layer: with alundum (Al2O3) powder and glue mixing and stirring; spray to membrane surface; again barrier film is covered (sprayed coating and hot pressing graphite linings are fitted) on the hot pressing graphite linings; namely form insulating protective layer, insulation protection layer thickness 10 μ m after oven dry on hot pressing graphite linings surface.Wherein the certificate of alundum (Al2O3) powder and glue is to decide according to the insulation protection layer thickness to consumption, and alundum (Al2O3) powder and glue used by weight 1: 1, PVDF content 10% (mass percentage content) in glue, and all the other are acetone.
Embodiment 3
Adopt the preparation method of embodiment 1 to prepare multi-layer composite electrode, difference is the preparation employing following steps of high-capacity metal lithium powder composite cathode:
Under the argon gas atmosphere protection, 95 gram toluene and 4.5 gram vinylacetate mixing and stirring are obtained glue; 15 gram lithium metal powders, 75 gram tin powder, 5 gram carbon nano-tube are joined in glue, be sprayed into the conductive adhesive layer surface after stirring, the preparation of high-capacity metal lithium powder composite cathode is namely completed in oven dry and rolling under 160 ℃ of conditions on the conductive adhesive layer surface.
Embodiment 4
Adopt the preparation method of embodiment 1 to prepare multi-layer composite electrode, difference is the preparation employing following steps of high-capacity metal lithium powder composite cathode:
Under the argon gas atmosphere protection, 45 gram acetone and 4.5 gram Kynoar mixing and stirring are obtained glue; 10 gram lithium metal powder 77 gram Si powder, 1.5 gram acetylene blacks and 1.5 gram carbon nano-tube are joined in glue, be sprayed into the conductive adhesive layer surface after stirring, the preparation of high-capacity metal lithium powder composite cathode is namely completed in oven dry and rolling under 140 ℃ of conditions on the conductive adhesive layer surface.
Claims (5)
1. a multi-layer composite electrode, is characterized in that, by forming as lower floor's structure of distributing successively:
(a) collector;
(b) conductive adhesive layer;
(c) high-capacity metal lithium powder composite cathode;
(d) hot pressing graphite linings;
(e) insulating protective layer that is formed by metal oxide, the thickness of insulating protective layer are 0.1-20 μ m; Wherein,
Described collector is electrolytic copper foil, rolled copper foil, copper mesh or carbon paper tinsel;
The conducting resinl that described conductive adhesive layer adopts following weight portion to form makes:
(A) glue is 40 parts;
(B) electrocondution slurry is 60 parts;
The weight portion of wherein said (A) glue consists of:
60～83 parts of Sodium Polyacrylates;
16～40 parts, water;
Ca(OH)
25 parts;
The weight portion of described (B) electrocondution slurry consists of:
5～55 parts of acetylene blacks;
45～94 parts, water;
Described high-capacity metal lithium powder composite cathode, its weight portion consists of:
1～80 part of metallic lithium powder;
10～90 parts, negative pole powder;
1～10 part of conductive agent;
1～4.5 part of binding agent;
0～0.5 part, surfactant;
Described negative pole powder is one or more in the oxide of oxide, silicon, silicon of graphite, soft carbon, hard carbon, tin, tin;
Described conductive agent is one or more in acetylene black, electrically conductive graphite, carbon nano-tube, carbon fiber;
Described binding agent is one or more in Kynoar, polytetrafluoroethylene, vinylacetate;
The metal oxide that is used to form described insulating protective layer is Al
2O
3, ZrO
2, TiO
2Or MgO.
2. multi-layer composite electrode as claimed in claim 1, is characterized in that, described (c) high-capacity metal lithium powder composite cathode, and its weight portion consists of:
10～50 parts of metallic lithium powders;
40～90 parts, negative pole powder;
3～8 parts of conductive agents;
1～4.5 part of binding agent;
0.2～0.5 part, surfactant.
3. multi-layer composite electrode as claimed in claim 2, is characterized in that, described (c) high-capacity metal lithium powder composite cathode, and its weight portion consists of:
10～30 parts of metallic lithium powders;
60～80 parts, negative pole powder;
2～5 parts of conductive agents;
1～4.5 part of binding agent;
0.2～0.5 part, surfactant.
4. multi-layer composite electrode as described in one of claim 1-3, it is characterized in that, the preparation method of described (c) high-capacity metal lithium powder composite cathode is, metallic lithium powder, negative pole powder, surfactant and conductive agent are carried out mix and blend under inert atmosphere, obtain finely dispersed mixture, this mixture is joined mix and blend in glue, obtains slurry after being uniformly dispersed, and the slurry drying obtains described high-capacity metal lithium powder composite cathode;
Described glue is by described binding agent and solvent composition, and described solvent is toluene, hexane, heptane, dimethylbenzene or acetone.
5. the preparation method of multi-layer composite electrode as claimed in claim 1, is characterized in that, comprises at first and covering conductive adhesive layer at collection liquid surface, then successively formation high-capacity metal lithium powder composite cathode, hot pressing graphite linings and insulating protective layer.
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