CN102201565A - 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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- CN102201565A CN102201565A CN2011100935373A CN201110093537A CN102201565A CN 102201565 A CN102201565 A CN 102201565A CN 2011100935373 A CN2011100935373 A CN 2011100935373A CN 201110093537 A CN201110093537 A CN 201110093537A CN 102201565 A CN102201565 A CN 102201565A
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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 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 improving the charge-discharge performance of battery, satisfy market demands, 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 mainly be with carbon materials as negative pole, 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 Chang Gui graphite cathode energy density is low is 372mAh/g only, 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 influenced 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 an atomic weight minimum (6.94) in the metal, 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 form dendrite in the relatively poor and cyclic process of its chemical stability, pierce through barrier film easily, cause the cell safety problem, can't satisfy 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 the electrolyte
2, Al
2O
3Wait the problem of improving dendrite (referring to Kanamura K, Okagawa T, Takehara z.J.Power Sources, 1995, carry out cycle performance and the security performance that coating modification improves lithium anode 57:119-123) or 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 the 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 owing to contact between particle is loose, contact resistance is bigger, and in the repeated charge process, the metallic lithium powder particle is grown up gradually, has lost the advantage of powdered.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 the 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 with 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 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 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 lithium metal powder forms in the repeated charge process 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 material mixing such as oxide, tin and oxide thereof thereof are prepared composite negative pole, thereby improve the specific capacity of negative pole.And save the specific capacity of negative pole to adapt to anodal needs by the adjustable ratio of adjusting negative materials such as lithium metal powder and carbon, tin, silicon within the specific limits.By applying insulating protective layer, prevent that further Li dendrite from piercing through barrier film and causing internal short-circuit in addition, improve the security performance of battery at electrode surface.The present invention also provides the application conditions of metallic lithium powder composite negative pole, because pole piece assembling pressure and inner pressure of battery have very big influence to the growth of Li dendrite, by increasing electrode assembling pressure and increasing the growth that inner pressure of battery can effectively suppress Li dendrite, therefore utilize the relative traditional lithium ion battery of pressure of metallic lithium powder composite negative pole assembled battery bigger with inner pressure of battery.
A kind of high power capacity metallic lithium powder composite negative pole, its weight portion consists of:
1～80 part of metallic lithium powder;
10～90 parts in negative pole powder;
1～10 part of conductive agent;
1～4.5 part of binding agent;
0～0.5 part in surfactant.
Wherein surfactant is a selectable components, certainly as preferred, and interpolation surfactant that can be an amount of.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 power capacity metallic lithium powder composite negative pole, its weight portion consists of:
10～50 parts of metallic lithium powders;
40～90 parts in negative pole powder;
3～8 parts of conductive agents;
1～4.5 part of binding agent;
0.2～0.5 part in surfactant.
As further preferred, described high power capacity metallic lithium powder composite negative pole, its weight portion consists of:
10～30 parts of metallic lithium powders;
60～80 parts in negative pole powder;
2～5 parts of conductive agents;
1～4.5 part of binding agent;
0.2～0.5 part in 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, the carbon fiber.
Described lithium metal powder can be the metallic lithium powder that commercially available surface coats stabilized zone, the perhaps lithium metal powder by the CVD (Chemical Vapor Deposition) method preparation, 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 negative poles such as Si.
Described binding agent is one or more in Kynoar (PVDF), polytetrafluoroethylene (PTFE), the vinylacetate (EVA).
At the binding agent described in the actual fabrication process is to be dispersed in the solvent of volatilizable type the form with glue to use one or more in the solvent of volatilizable type such as toluene, hexane, heptane, dimethylbenzene, the 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.
Because solvent needs the oven dry volatilization in subsequent process, generally product there is not substantial effect, therefore the not strict restriction of the consumption of solvent, but in order to make binding agent and other raw materials energy good mixing and dispersion, weight of solvent generally can be 5～100 times of weight of binder.
The present invention also provides a kind of preparation method of described high power capacity metallic lithium powder composite negative pole, comprise: metallic lithium powder, negative pole powder and conductive agent are mixed stirring under inert atmosphere, obtain finely dispersed mixture, this mixture joined in the glue to mix obtain slurry after stirring, being uniformly dispersed, the slurry drying obtains described high power capacity metallic lithium powder composite negative pole.
Described glue is by described binding agent and solvent composition, and 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 generally can be 5～100 times of weight of binder.
Because 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 the collection liquid surface of band conductive adhesive layer by methods such as transfer coated or sprayings, drying, obtain described high power capacity metallic lithium powder composite negative pole after rolling.
The temperature range of described oven dry is 90～160 ℃, also can adopt vacuum drying to promote the volatilization of solvent with this understanding.
As preferably, when preparation mixture and slurry, all under inert atmosphere protections such as argon gas, to carry out, used mixing is stirred and is adopted mechanical mixture.
The present invention also provides a kind of MULTILAYER COMPOSITE electrode, by becoming of distributing successively as lower floor's structural group:
(a) collector;
(b) conductive adhesive layer;
(c) described high power capacity metallic lithium powder composite negative pole;
(d) hot pressing graphite linings;
(e) insulating protective layer that forms by metal oxide;
Described collector can adopt prior art, for example can be 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 in 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 in the water of solvent.
Each component and also can adopt other schemes of the prior art in the conducting resinl with magnitude relation.
The present invention also provides a kind of preparation method of described MULTILAYER COMPOSITE electrode, comprises at first and is covering conductive adhesive layer at collection liquid surface, then formation high power capacity metallic lithium powder composite negative pole, hot pressing graphite linings and insulating protective layer successively.
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 of being with conductive adhesive layer.
Can be in the described high power capacity metallic lithium powder composite negative pole by the ratio of raw material, the specific capacity that changes negative pole is to adapt to anodal needs.
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 portions the about 1051mAh/g of the capacity of negative plates that obtains.
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 on the described high power capacity metallic lithium powder composite negative pole (the plastics foil is peeled off removal after hot pressing), 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, the carbon fiber.The weight ratio of graphite granule and conductive agent is 10～30: 1.
Described PVDF emulsion can adopt the commercially available prod, be dispersant with acetone for example, the mass percentage content of PVDF is 1～10% in the emulsion, and same described PTFE emulsion also can adopt the commercially available prod, be dispersant with water for example, the mass percentage content of PTFE is 1～10% in the emulsion.
When preparing described hot pressing graphite linings, because dispersant can be adjusted in a big way in the emulsion, therefore the not strict restriction of the weight ratio of graphite granule and binding agent, the weight ratio of PVDF or PTFE can be 1: 0.03～0.3 in general graphite granule and the emulsion.
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 metal oxide such as MgO.
Preparation joins oxide during insulating protective layer and is applied to the graphite linings surface in the glue after the dispersed with stirring, and oven dry (90～140 ℃ of temperature) at last removes desolvates.
Insulating protective layer is selected oxide ceramic material for use on raw material, form loose structure on the microcosmic.Insulating protective layer can be coating and to cover on the graphite linings surface also can be to be coated on the barrier film.Be coated in when using on the barrier film, covering in the lump on the graphite linings surface, and insulating protective layer is adjacent with the graphite linings surface together with barrier film.
The glue that the glue that preparation is adopted during insulating protective layer adopts in the time of can adopting the described high power capacity metallic lithium powder composite negative pole of preparation for example adopts the acetone that contains Kynoar (PVDF) etc.
During the preparation insulating protective layer, because solvent can be adjusted in a big way in the glue, so the not strict restriction of the weight ratio of metal oxide and glue, the weight ratio of solute can be 1: 0.03～0.3 in common metal oxide and the glue.
As preferably, adopt Al
2O
3Be feedstock production insulating protective layer, Al
2O
3Can with the reactions such as PC, EC in the electrolyte, help generating effective passivating film on lithium metal powder surface, suppress the growth of Li dendrite.
The inner pressure of battery of the assembling pressure of the MULTILAYER COMPOSITE electrode described in the present invention and this MULTILAYER COMPOSITE electrode preparation of use is higher, can suppress the growth of lithium metal dendrite.
Each layer structure in the described MULTILAYER COMPOSITE electrode, if there is not specified otherwise, its thickness does not have strict restriction, can be according to prior art or actual demand design.
The present invention reduces the active material consumption and improves the battery specific capacity by the specific discharge capacity and the volume and capacity ratio of lithium metal powder and graphite, soft carbon, hard carbon, tin and the compound raising negative materials of material such as oxide, silicon and oxide thereof thereof; 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 negative materials such as graphite, hard carbon, soft carbon, tin, silicon.
Description of drawings
Fig. 1 is the structural representation of MULTILAYER COMPOSITE electrode of the present invention.
Embodiment
Embodiment 1
The preparation of high power capacity metallic lithium powder composite negative pole: the argon gas atmosphere protection down; 30 toluene and 4.5 Kynoar (PVDF) that restrain as binding agent that restrain as solvent are mixed and made into glue; 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 the glue as the acetylene black of conductive agent; be sprayed into the collection liquid surface that has conductive adhesive layer after stirring; (promptly be sprayed into the conductive adhesive layer surface; the collector that wherein has conductive adhesive layer can utilize prior art for preparing or commercial); dry under 120 ℃ of conditions and roll; promptly finish the preparation of high power capacity metallic lithium powder composite negative pole on the conductive adhesive layer surface, the specific capacity of the high power capacity metallic lithium powder composite negative pole for preparing after testing can reach 1315mAh/g.
Embodiment 2
Referring to Fig. 1, a kind of MULTILAYER COMPOSITE electrode is made of the collector 1, conductive adhesive layer 2, high power capacity metallic lithium powder composite negative pole 3, hot pressing graphite linings 4, insulating protective layer 5 and the barrier film 6 that distribute successively.Its preparation method is as follows:
Have the preparation of the collector of conductive adhesive layer: the Copper Foil of getting thickness and be 10 μ m is 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 that gets ready and add to mix in the 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 having the collector of conductive adhesive layer, and it is stand-by to reel.
The preparation of high power capacity metallic lithium powder composite negative pole:
The argon gas atmosphere protection down; 30 toluene and 4.5 Kynoar (PVDF) that restrain as binding agent that restrain as solvent are mixed and made into glue; 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 the 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; promptly finish the preparation of high power capacity metallic lithium powder composite negative pole on the conductive adhesive layer surface, the specific capacity of this high power capacity metallic lithium powder composite negative pole 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 the acetylene black and 50 grams of 2.5 grams as conductive agent, stir and be coated in plastics foil surface, oven dry obtains graphite linings, the graphite linings that obtains is hot-pressed onto the surface of high power capacity metallic lithium powder composite negative pole, hot pressing temperature is 160 ℃, peels off the plastics foil then.Wherein the PVDF emulsion is a dispersant with acetone, and the mass percentage content of PVDF is 5% in the emulsion.High power capacity metallic lithium powder composite negative pole 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 (Al 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; promptly form insulating protective layer, insulation protection layer thickness 10 μ m after the oven dry on hot pressing graphite linings surface.Wherein the certificate of alundum (Al powder and glue is to decide according to the insulation protection layer thickness to consumption, and alundum (Al powder and glue used by weight 1: 1, PVDF content 10% (mass percentage content) in the glue, and all the other are acetone.
Embodiment 3
Adopt the preparation method of embodiment 1 to prepare the MULTILAYER COMPOSITE electrode, difference is the preparation employing following steps of high power capacity metallic lithium powder composite negative pole:
The argon gas atmosphere protection obtains glue with 95 gram toluene and 4.5 gram vinylacetate mixing and stirring down; 15 gram lithium metal powders, 75 gram tin powder, 5 gram carbon nano-tube are joined in the glue, be sprayed into the conductive adhesive layer surface after stirring, dry under 160 ℃ of conditions and roll, promptly finish the preparation of high power capacity metallic lithium powder composite negative pole on the conductive adhesive layer surface.
Embodiment 4
Adopt the preparation method of embodiment 1 to prepare the MULTILAYER COMPOSITE electrode, difference is the preparation employing following steps of high power capacity metallic lithium powder composite negative pole:
The argon gas atmosphere protection obtains glue with 45 gram acetone and 4.5 gram Kynoar mixing and stirring down; 10 gram lithium metal powders, 77 gram Si powder, 1.5 gram acetylene blacks and 1.5 gram carbon nano-tube are joined in the glue, be sprayed into the conductive adhesive layer surface after stirring, dry under 140 ℃ of conditions and roll, promptly finish the preparation of high power capacity metallic lithium powder composite negative pole on the conductive adhesive layer surface.
Claims (9)
1. high power capacity metallic lithium powder composite negative pole is characterized in that its weight portion consists of:
1～80 part of metallic lithium powder;
10～90 parts in negative pole powder;
1～10 part of conductive agent;
1～4.5 part of binding agent;
0～0.5 part in 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, the carbon fiber;
Described binding agent is one or more in Kynoar, polytetrafluoroethylene, the vinylacetate.
2. the described high power capacity metallic lithium powder of claim 1 composite negative pole is characterized in that, its weight portion consists of:
10～50 parts of metallic lithium powders;
40～90 parts in negative pole powder;
3～8 parts of conductive agents;
1～4.5 part of binding agent;
0.2～0.5 part in surfactant.
3. the described high power capacity metallic lithium powder of claim 2 composite negative pole is characterized in that, its weight portion consists of:
10～30 parts of metallic lithium powders;
60～80 parts in negative pole powder;
2～5 parts of conductive agents;
1～4.5 part of binding agent;
0.2～0.5 part in surfactant.
4. as the preparation method of each described high power capacity metallic lithium powder composite negative pole of claim 1～3, it is characterized in that, metallic lithium powder, negative pole powder and conductive agent are mixed stirring under inert atmosphere, obtain finely dispersed mixture, this mixture joined in the glue to mix obtain slurry after stirring, being uniformly dispersed, the slurry drying obtains described high power capacity metallic lithium powder composite negative pole;
Described glue is by described binding agent and solvent composition, and described solvent is toluene, hexane, heptane, dimethylbenzene or acetone.
5. a MULTILAYER COMPOSITE electrode is characterized in that, by becoming of distributing successively as lower floor's structural group:
(a) collector;
(b) conductive adhesive layer;
(c) as each described high power capacity metallic lithium powder composite negative pole of claim 1～3;
(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.
6. MULTILAYER COMPOSITE electrode as claimed in claim 5 is characterized in that, described collector is electrolytic copper foil, rolled copper foil, copper mesh or carbon paper tinsel.
7. MULTILAYER COMPOSITE electrode as claimed in claim 6 is characterized in that, 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 in water;
Ca (OH)
25 parts;
The weight portion of described (B) electrocondution slurry consists of:
5～55 parts of acetylene blacks;
45～94 parts in water.
8. MULTILAYER COMPOSITE electrode as claimed in claim 6 is characterized in that, the metal oxide that is used to form described insulating protective layer is AI
2O
3, ZrO
2, TiO
2Or MgO.
9. as the preparation method of each described MULTILAYER COMPOSITE electrode of claim 5～8, it is characterized in that, comprise at first and covering conductive adhesive layer, then formation high power capacity metallic lithium powder composite negative pole, hot pressing graphite linings and insulating protective layer successively at collection liquid surface.
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