CN1427490A - Dispersion of lithium metal in anode of secondarycell - Google Patents

Dispersion of lithium metal in anode of secondarycell Download PDF

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Publication number
CN1427490A
CN1427490A CN02124684A CN02124684A CN1427490A CN 1427490 A CN1427490 A CN 1427490A CN 02124684 A CN02124684 A CN 02124684A CN 02124684 A CN02124684 A CN 02124684A CN 1427490 A CN1427490 A CN 1427490A
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anode
lithium
host material
secondary cell
lithium metal
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CN1290209C (en
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Y·高
J·L·博巴三世
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Levent Usa
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FMC Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention is a secondary battery having a high specific capacity and good cycleability, and that can be used safely. The secondary battery is manufactured to include an anode formed from a host material capable of absorbing and desorbing lithium in an electrochemical system such as a carbonaceous material, and lithium metal dispersed in the host material. The freshly prepared anodes of the invention are combined with a positive electrode including an active material, a separator that a separates the positive electrode and the negative electrode, and an electrolyte in communication with the positive electrode and the negative electrode. The present invention also includes a method of preparing a freshly prepared anode and a method of operating a secondary battery including the anode of the invention.

Description

The dispersion of lithium metal in the secondary cell anode
The related application of reference
It is 60/257,994 that the application relates to the series number that the applicant owns together, and the applying date is the provisional application just on the docket on December 22nd, 2000, and requires the rights and interests of the application according to the earlier application day of 35 U.S.C. § 119 (e).
Invention field
The present invention relates to have the secondary cell of height ratio capacity, relate to the anode of secondary cell especially, this anode contain such as can be in electro-chemical systems the host material of the carbonaceous material of absorption and desorption lithium, and the lithium metal that in host material, disperses.
Background of invention
Secondary cell or the rechargeable battery of recently having found lithium and lithium ion can be with in some applications, for example, portable phone, camcorder and kneetop computer, even more be used to recently in the high-power applications such as motor vehicle and hybrid electric vehicles.In these were used, preferably, this secondary cell had the highest as far as possible specific capacity, but still safe operating condition and good circulation ability can be provided, so as afterwards recharge with discharge cycles in can keep this height ratio capacity.
Though secondary cell has various structures, every kind of structure all comprises positive electrode (or negative electrode), negative electrode (or anode) and the division board that negative electrode and anode are separated, and the electrolyte that keeps electrochemistry to get in touch with negative electrode and anode.For serondary lithium battery, when this secondary cell discharged, when promptly using in concrete the application, lithium ion was transferred to negative electrode by electrolyte from anode.During this process, electronics compiles and is delivered to negative electrode by external circuit from anode.When this secondary cell was recharged or recharged, lithium ion was transferred to anode by electrolyte from negative electrode.
In the past, serondary lithium battery was to use the compound that does not carry out lithia chemical combination (non-lithiated) with height ratio capacity, for example TiS 2, MoS 2, MnO 2And V 2O 5Produce as active material of cathode.These active material of cathode and lithium anodes pairing are used.When this secondary cell discharged, lithium ion was transferred to negative electrode by electrolyte from the anode of lithium metal.Yet at circulation time, this lithium metal produces the dendrite that finally can cause unsafe condition in battery.Therefore, just stopped producing the secondary cell of these types at the initial stage in generation nineteen ninety, and adopted lithium ion battery.
Lithium ion battery generally uses such as LiCoO 2And LiNiO 2Lithium metal oxide as the active material of cathode that is used with carbon based anode.In these batteries, avoided the generation of lithium dendrite on anode, thereby made this battery safer.Yet, this lithium, its quantity has determined the capacity of battery, all is to be provided by negative electrode, this has just limited the selection of active material of cathode, because this active material must contain movably lithium.In addition, at charging (for example, Li xCoO 2And Li xNiO 2, 0.4＜x＜1.0 wherein) or (for example, the Li that overcharges xCoO 2And Li xNiO 2, x＜0.4 wherein) during form and LiCoO 2And LiNiO 2The corresponding product that takes off lithia chemical combination (delithiated) is unsettled.Specifically, these take off product easy and the electrolyte reaction and the generation heat of lithia chemical combination, and it causes the concern to fail safe.
Summary of the invention
The present invention is a kind of have height ratio capacity and good circulation ability and secondary cell that can safety operation.According to the present invention, the secondary cell of this prepared fresh comprise by can be in electro-chemical systems the host material of absorption and desorption lithium and the anode that the lithium metal that disperses in host material is formed.Preferably, this lithium metal is fine lithium powder, and more preferably it has less than about 20 microns average particle size particle size.This host material comprises one or more materials that are selected from the group that is made of carbonaceous material, Si, Sn, tin-oxide, compound ashbury metal, transition metal oxide, metal lithium nitride and lithium metal oxide.Preferably, this host material comprises carbonaceous material, more preferably comprises graphite.
The secondary cell of the present invention of this prepared fresh comprises the positive electrode that contains active material, contain in electro-chemical systems matrix material system that can the absorption and desorption lithium and the negative electrode of the lithium metal that disperses in host material, dividing plate that positive electrode and negative electrode are separated, and with the electrolyte of positive electrode and negative electrode UNICOM.Preferably, active material of cathode be a kind of be can carry out the compound of lithia chemical combination (lithiated) at 0.2 to 0.5 o'clock at the relative electrochemical potentials of lithium.For example, active material of cathode can be MnO 2, V 2O 5Or MoS 2, or their mixture.At preferably a kind of fine lithium powder of the lithium metal of anode, more preferably have less than about 20 microns average particle size particle size.Host material comprises one or more materials that are selected from the group that is made of carbonaceous material, Si, Sn, tin-oxide, compound ashbury metal, transition metal oxide, metal lithium nitride and lithium metal oxide.Preferably, comprise carbonaceous material, more preferably comprise graphite at the host material of negative electrode.The quantity that is present in the lithium metal of negative electrode preferably is not more than the quantity that is enough to the maximum that sandwiches, fuse or be absorbed in the host material of negative electrode.For example, if host material is a carbon, then the quantity of lithium preferably is not more than and generates LiC 6Needed quantity.
The present invention also comprises a kind of preparation method of secondary cell anode of prepared fresh, it comprise provide a kind of can be in electro-chemical systems the host material of absorption and desorption lithium, in host material, disperse the lithium metal, with host material be dispersed in its inner lithium metallic and become the step of anode.Preferably lithium metal and host material and on-aqueous liquid are mixed to produce a kind of slurries, subsequently it is coated on the collector electrode and dry to form anode.In addition, anode can prepare by chemical method, and it is by host material being immersed in the lithium metal in a kind of suspension of on-aqueous liquid, making anode then.
The present invention further comprises a kind of method of operating secondary cell.At first, freshly prepared secondary cell is provided, it comprises the positive electrode that contains active material, contain can be in electro-chemical systems the negative electrode, the dividing plate that positive electrode and negative electrode are separated of the host material of absorption and desorption lithium and the lithium metal that in host material, disperses, and with the electrolyte of positive electrode and negative electrode UNICOM.Specifically, this secondary cell is to make with the lithium metal in the host material that is dispersed in anode.The battery of this fresh assembling is to be in the electric state that filled, and more preferably is to be in to have filled electric state (being present in all lithiums movably in the anode of this freshly prepared battery) fully.This freshly prepared secondary cell is to begin discharge by lithium ion is sent to positive electrode from negative electrode through electrolyte.Then, this secondary cell can charge or recharges by lithium ion is sent to negative electrode from positive electrode through electrolyte, once more lithium ion is sent to positive electrode from negative electrode through electrolyte subsequently and discharges.The step generation that can repeatedly circulate of charging and discharge, and can keep the height ratio capacity of active material of cathode and keep safe operating condition.
These and other characteristic and advantage of the present invention, concerning those those skilled in the art, (it has described preferred and alternative embodiment of the present invention) will be understood easilier after having investigated following detailed and accompanying drawing.
The simple description of accompanying drawing
Fig. 1 has described a kind of structure of the secondary cell according to simplification of the present invention, and it comprises negative electrode, anode, dividing plate and electrolyte.
The detailed description of the preferred embodiment of the invention
Accompanying drawing and below detailed description in, describe a kind of embodiment preferred in detail, so that implement the present invention.Though the present invention describes with reference to these specific preferred embodiments, should be appreciated that the present invention is not restricted to these embodiment preferred.On the contrary, the present invention includes many alternative, improved and equivalent embodiments, consider to become clearer behind following detailed and the accompanying drawing.
As described in Figure 1, the present invention is a kind of secondary cell 10, and it comprises positive electrode or negative electrode 12, negative electrode or anode 14, the dividing plate 16 that positive electrode and negative electrode are separated and the electrolyte that is communicated with positive electrode and negative electrode.This secondary cell 10 also comprises collector electrode 20, and it contacts with cathodic electricity and another collector electrode 22, and it and anode electrically contact. Collector electrode 20 and 22 is electrical contact with each other by the external circuit (not shown).This secondary cell 10 can have any structure well known in the art, such as " colloid cartridge type " (" jelly roll ") or stacked (stack) structure.
Negative electrode 12 is made by active material, and its general and carbonaceous material and binder polymer combine.Be used for the active material of negative electrode 12 preferably a kind of under effective voltage (being 2.0 to 5.0 volts for example) to lithium can carry out the material of lithia chemical combination.Preferably, such as MnO 2, V 2O 5Or MoS 2, or the material of the such non-lithiaization of their mixture can be used as this active material, and more preferably, use MnO 2But, all LiMn that if can further carry out lithia chemical combination 2O 4The material that has carried out lithia chemical combination, also can be used.This active material of lithia chemical combination that do not carry out is by preferred, because they than those active materials of having carried out lithia chemical combination have higher specific capacity usually, thereby can provide more electric power than those secondary cells that comprise the active material that carries out lithia chemical combination in this structure.In addition, because anode 14 comprises lithium, as described below, the negative electrode 12 of secondary cell 10 comprises that the lithia combination materials is unnecessary to operation.Preferably enough accept to be present in movably lithium on the anode 14 in the quantity of the active material that negative electrode 12 provides.For example,,, preferably in negative electrode 12, there is one mole MnO2, so that produce LiMnO at negative electrode during discharge so for the lithium of each mole in anode 14 if MnO2 is an active material of cathode 2
Aforesaid can carry out the active material of cathode of lithia chemical combination the time when using, the movably lithium that is recycled in battery is all provided by anode 14, and as preferred version, and this battery is assembled or is mixed with and is in complete charged state.Yet negative electrode 12 can also comprise that a spot of one or more have carried out the active material (LiCoO for example of lithia chemical combination 2And LiNiO 2), they further do not absorb lithium under 2.0 volts to 5.0 volts voltage, and this battery still can be provided as being in initial state of charge.In this case, negative electrode preferably has the material that more preferably has less than 50% (mole) less than the chemical combination of lithia of 10% (mole) (LiCoO for example 2And LiNiO 2) as active material.Because LiCoO 2And LiNiO 2Further do not absorb lithium, the existence of these materials does not reduce and receives the movably quantity of the needed active material of cathode of lithium from anode 14 in negative electrode 12.
Anode 14 is to be made by host material 24 that can the absorption and desorption lithium in electro-chemical systems, is dispersed with lithium metal 26 in described host material.For example, when battery (particularly anode) when recharging, the lithium that exists in anode 14 can sandwich in host material, fuses or be absorbed.This host material is included in the material of energy absorption and desorption lithium in the electro-chemical systems, for example carbonaceous material; The material that contains Si, Sn, tin-oxide or compound ashbury metal; Transition metal oxide, for example CoO; Metal lithium nitride, for example Li 3-xCo xN, wherein 0＜x＜0.5, and lithium metal oxide, for example Li 4Ti 5O 12This lithium metal 26 preferably offers anode 14 with fine lithium powder form.In addition, the average particle size particle size that this lithium metal 26 preferably has is less than about 20 microns, more preferably less than about 10 microns.This lithium metal can be pyrophoric powder or stable low incendivity powder, for example, by using the carbon dioxide treatment lithium metal powder, form provide.
With respect to the lithium metal from greater than 0.0 volt to being less than or equal under 1.5 volts the electrochemical potentials, this anode 14 generally can reversibly carry out lithia chemical combination and take off lithia chemical combination.If the electrochemical potentials to lithium is less than or equal to 0.0, so this lithium metal can not reenter anode 14 when charging.On the other hand, if to the electrochemical potentials of lithium greater than 1.5 volts, the voltage of battery will be undesirable low so.Preferably, the quantity that is present in the lithium metal 26 in the anode 14 is not more than is enough to the maximum quantity that sandwiches, fuse or be absorbed in the host material of anode 14 when battery is recharged.For example, if host material 24 is a carbon, the quantity of lithium 26 preferably is not more than is enough to produce LiC 6Quantity.In other words, the mol ratio of lithium and carbon preferably is not more than 1: 6 in this anode.
According to the present invention, anode 14 can by be provided in the electro-chemical systems can the absorption and desorption lithium host material, in host material, disperse the lithium metal, and this host material and the lithium formation anode that disperses therein prepared.Preferably, mix with lithium metal and host material and such as the on-aqueous liquid and the adhesive of tetrahydrofuran, and make slurries.Use this slurries to prepare anode 14 then, for example, this slurries are coated on the collector electrode 22, dry these slurries then.Also can contain in the suspension of lithium metal, the lithium metal is provided in the anode by host material being immersed at on-aqueous liquid such as hydrocarbon solvent (for example hexane).As mentioned above, the lithium metal that uses in this suspension is preferably fine lithium powder.This host material can be made into the shape of anode, immerses then in the suspension of lithium metal, and perhaps it can combine to generate a kind of slurries with the suspension of lithium metal, is coated on the collector electrode then, and is dried to make anode.This on-aqueous liquid that is used for supending can pass through dry anode (for example, under elevated temperature) and remove.No matter but how make, the lithium metal is distributed in the host material preferably as well as possiblely.Therefore, as mentioned above, the average particle size particle size that lithium metal 26 preferably has is less than about 20 microns, more preferably less than about 10 microns.
Host material 24 in the anode 14 can comprise one or more can be in electro-chemical systems the material of absorption and desorption lithium, for example carbonaceous material; The material that contains Si, Sn, tin-oxide or compound ashbury metal; Transition metal oxide, for example CoO; Metal lithium nitride, for example Li 3-xCo xN, wherein 0＜x＜0.5; And lithium metal oxide, for example Li 4Ti 5O 12Preferably, as mentioned above, host material 24 preferably includes graphite.In addition, host material 24 preferably includes a spot of carbon black (for example less than 5 weight %) as conductive agent.
As shown in Figure 1, negative electrode 12 separates with anode 14 by electric insulation baffle 16.Usually, dividing plate 16 is by making such as the material of polyethylene, polypropylene or polyvinylidene fluoride (PVDF).
Secondary cell 10 further comprises electrolyte, and it and negative electrode 12 and anode 14 remain in electrochemistry UNICOM.This electrolyte can be non-water liquid, gelinite or solid, preferably includes lithium salts, for example LiPF 6Electrolyte is provided in the entire cell 10, especially in negative electrode 12, anode 14 and dividing plate 16.Usually, this electrolyte is liquid, and negative electrode 12, anode 14 and dividing plate 16 are to be immersed in the electrolyte so that the porous material of electrochemistry UNICOM to be provided at these inter-modules.
As mentioned above, battery 10 comprises collector electrode 20 and 22, and they are used to transmit electronics to external circuit.Preferably, collector electrode 20 is made by aluminum slice, and collector electrode 22 is made by copper foil.
Battery 10 of the present invention can prepare with method well known in the art, and preferably has layer thickness in following scope (in Fig. 1 from left to right):
Layer thickness
Collector electrode (20) 20-40 μ m
Negative electrode (12) 70-100 μ m
Dividing plate (16) 25-35 μ m
Anode (14) 70-100 μ m
Collector electrode (22) 20-40 μ m
Battery 10 also is included in the electrolyte that disperses in negative electrode 12, anode 14 and the dividing plate 16, and shell (not shown).
When operation, this freshly prepared secondary cell 10 is initially in a kind of electric state that filled, more preferably be to be in to have filled electric state fully, and by through electrolyte lithium ion being sent to negative electrode 12 by initial discharge from anode 14.Simultaneously, by collector electrode 22, external circuit and collector electrode 20 electronics is sent to negative electrode 12 from anode 14.Then, secondary cell 10 can charge or recharges by lithium ion is sent to anode 14 from negative electrode 12 through electrolyte, is discharged as mentioned above then again.The generation that can repeatedly circulate of the step of this charging and discharge, and can keep the height ratio capacity of active material of cathode and keep safe operating condition.
Secondary cell 10 can be used in various types of application.For example, this secondary cell can be used to mancarried electronic aid, as portable phone, field camera and kneetop computer, and is used for high-power applications, such as in motor vehicle and the hybrid electric vehicles.
The invention provides have height ratio capacity, the secondary cell of the operating condition of safety and good circulation ability.Specifically, because provide the lithium metal at anode, the material that does not carry out lithia chemical combination in secondary cell can be used as preferred active material of cathode.These materials that do not carry out lithia chemical combination have higher specific capacity than the material that carries out lithia chemical combination that uses at present in lithium ion battery.Have the active material of cathode that do not carry out lithia chemical combination and a lithium secondary battery of lithium metal anode unlike traditional, the secondary cell of having found to use the active material of cathode that does not carry out lithia chemical combination that combines with anode of the present invention to produce can be operated safely and can not produce Li dendrite at circulation time.In addition, secondary cell of the present invention is more safer than lithium ion battery operation because the latter between charge period when the instability that when negative electrode moves lithium ion, can become.Specifically, when battery during by fresh preparation, because the active material of cathode in the secondary cell of the present invention generally is to be in the state of charging fully, so it is more stable than the cathode material that uses at lithium ion battery.In addition, battery of the present invention can be recharged and discharge heap of times, and can keep the safe operating condition and the height ratio capacity of active material of cathode.
Should be appreciated that read the above-mentioned description of this invention and investigated accompanying drawing after, those skilled in the art can therefrom modify and change.But these modifications and variations all are included in the spirit and scope of appended claims.

Claims (40)

1. the anode of the secondary cell of a prepared fresh, comprise a kind of can be in electro-chemical systems the host material of absorption and desorption lithium and the lithium metal that in host material, disperses.
2. according to the anode of claim 1, wherein, the lithium metal is a kind of fine lithium powder.
3. according to the anode of claim 2, wherein, the average particle size particle size that lithium powder has is less than about 20 microns.
4. according to the anode of claim 1, with respect to the electrochemical potentials of lithium metal for greater than 0.0V when being less than or equal to 1.5V, can reversibly be carried out lithia chemical combination and be taken off lithia chemical combination.
5. according to the anode of claim 1, wherein, host material comprise one or more with respect to the electrochemical potentials of lithium for greater than 0.0V when being less than or equal to 1.5V, can reversibly carry out lithia chemical combination and take off the material of lithia chemical combination.
6. according to the anode of claim 1, wherein, host material comprises that one or more are selected from the material in the group that is made of carbonaceous material, Si, Sn, tin-oxide, compound ashbury metal, transition metal oxide, metal lithium nitride and lithium metal oxide.
7. according to the anode of claim 1, wherein, host material comprises carbonaceous material.
8. according to the anode of claim 7, wherein, carbonaceous material is a graphite.
9. according to the anode of claim 8, wherein, host material further comprises carbon black.
10. according to the anode of claim 1, wherein, the quantity of lithium metal is not more than the maximum quantity that enough sandwiches, fuses or be absorbed in the host material in described anode in the described anode when anode is recharged.
11. secondary cell that comprises the anode of claim 1.
12. the secondary cell of a prepared fresh comprises:
A kind of positive electrode that comprises active material;
A kind of comprise can be in electro-chemical systems the host material of absorption and desorption lithium and the negative electrode of the lithium metal that in host material, disperses;
A kind of dividing plate that positive electrode and negative electrode are separated; And
A kind of electrolyte with positive electrode and negative electrode maintenance UNICOM.
13. according to the secondary cell of claim 12, wherein, positive electrode comprises that a kind of electrochemical potentials at relative lithium can carry out the compound of lithia chemical combination as active material when being 2.0 to 5.0V.
14. according to the secondary cell of claim 13, wherein, the active material in the positive electrode is selected from by MnO 2, V 2O 5, MoS 2The group that constitutes with their mixture.
15. according to the secondary cell of claim 13, wherein, the active material of positive electrode comprises MnO 2
16. according to the secondary cell of claim 13, wherein, the active material of positive electrode is LiMn 2O 4
17. according to the secondary cell of claim 12, wherein, the lithium metal in described anode is fine lithium powder.
18. according to the secondary cell of claim 17, wherein, the average particle size particle size that the lithium metal in described anode has is less than about 20 microns.
19. according to the secondary cell of claim 12, wherein, anode with respect to the electrochemical potentials of lithium metal for greater than 0.0V when being less than or equal to 1.5V, can reversibly carry out lithia chemical combination and take off lithia chemical combination.
20. secondary cell according to claim 12, wherein, host material in described anode, comprise one or more electrochemical potentialses of relative lithium for greater than 0.0V when being less than or equal to 1.5V, can reversibly carry out lithia chemical combination and take off the material of lithia chemical combination.
21. secondary cell according to claim 12, wherein, the host material in described anode comprises that one or more are selected from the material in the group that is made of carbonaceous material, Si, Sn, tin-oxide, compound ashbury metal, transition metal oxide, metal lithium nitride and lithium metal oxide.
22. according to the secondary cell of claim 12, wherein, the host material in described anode comprises carbonaceous material.
23. according to the secondary cell of claim 22, wherein, carbonaceous material is a graphite.
24. according to the secondary cell of claim 23, wherein, host material further comprises carbon black.
25. according to the secondary cell of claim 12, wherein, the quantity of the lithium metal in described negative electrode is not more than the maximum quantity that enough sandwiches, fuses or be absorbed in the host material in described anode when described battery is recharged.
26. according to the secondary cell of claim 12, wherein, the quantity of the active material in described negative electrode enough accepts to be present in the movably lithium metal in the described anode.
27., be in a kind of electric state that filled fully according to the secondary cell of claim 12.
28. a method for preparing the anode of secondary cell comprises:
Provide a kind of can be in electro-chemical systems the host material of absorption and desorption lithium;
In host material, disperse the lithium metal; With
The lithium metal forming of host material and dispersion is therein made anode.
29. according to the method for claim 28, wherein, described dispersion steps comprises, lithium metal, host material and on-aqueous liquid are mixed to form slurries.
30. according to the method for claim 29, wherein, described forming step comprises, slurries are coated on the collector electrode, dry then these slurries.
31. according to the method for claim 28, wherein, described dispersion steps comprises host material is immersed in the suspension that contains lithium metal and on-aqueous liquid.
32. according to the method for claim 31, wherein, described dispersion steps comprises host material is immersed in the suspension of lithium metal in hydrocarbon.
33. according to the method for claim 28, wherein, described dispersion steps is included in the fine lithium metal powder of dispersion in the host material.
34. according to the method for claim 33, wherein, described dispersion steps is included in disperses average particle size particle size less than about 20 microns lithium metal in the host material.
35. method according to claim 28, wherein, the described step that provides comprises, a kind of host material is provided, this host material comprise one or more electrochemical potentialses of relative lithium for greater than 0.0V when being less than or equal to 1.5V, can reversibly carry out lithia chemical combination and take off the material of lithia chemical combination.
36. method according to claim 28, wherein, describedly provide step to comprise to provide a kind of host material, this host material to comprise that one or more are selected from the material in the group that is made of carbonaceous material, Si, Sn, tin-oxide, compound ashbury metal, transition metal oxide, metal lithium nitride and lithium metal oxide.
37., wherein, describedly provide step to comprise a kind of host material that comprises carbonaceous material is provided according to the method for claim 28.
38. according to the method for claim 37, wherein, described provide step to comprise a kind of its carbonaceous material to be provided be the host material of graphite.
39. according to the method for claim 38, wherein, describedly provide step to comprise a kind of host material is provided, wherein this host material further comprises carbon black.
40. a method of operating secondary cell comprises the steps:
(a) provide a kind of secondary cell of prepared fresh, it comprises the positive electrode that contains active material, contain can be in electro-chemical systems the host material of absorption and desorption lithium and the lithium metal that in host material, disperses negative electrode, the dividing plate that positive electrode and negative electrode are separated and keep the electrolyte of UNICOM with positive electrode and negative electrode;
(b) by being sent to positive electrode from negative electrode through electrolyte, lithium ion makes the secondary cell initial discharge;
(c) by being sent to negative electrode from positive electrode through electrolyte, lithium ion makes secondary cell charge;
(d) by being sent to positive electrode from negative electrode through electrolyte, lithium ion makes the secondary cell discharge;
(e) repeating step (c) and (d).
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