JP2002237334A - Double collector type negative electrode structure for alkaline metal ion battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stabilize electricity charging/discharging characteristic and to lengthen life by making initial irreversible capacity of a secondary battery can be compensated. SOLUTION: A 'sacrifice' alkaline metal part is formed in a portion of carbon system anode material as negative-electrode composition of a sandwiched type electrochemistry secondary battery. That is, the 'sacrifice' alkaline metal part of a lithium system is made to form in the anode material of hard carbon. Then, by compensating the initial irreversible nature of the electricity charging/ discharging, which is the problem of hard carbon, the excellent electricity- charging/discharging cycling characteristic that the hard carbon has, is employed efficiently, and the life of the conventional secondary battery is improved greatly.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to the conversion of chemical energy into electrical energy. In particular, the present invention
An anode material having an anode active material sandwiched between individual current collectors forms an intercalating and de-intercalating of the anode active material in contact with the opposite side of the current collector. A new anode design that can be done. INDUSTRIAL APPLICABILITY The negative electrode design of the present invention is useful as a secondary battery having a high discharge rate, such as a battery for supplying power to medical devices and devices that can be implanted in the body.

[0002]

2. Description of the Related Art Secondary electrochemical cells use carbon-based materials (cars).
bonaceous material) and lithium-based material (lithiat)
ed material) and is usually assembled in a discharged state. Then a reverse voltage is applied to this battery,
Migration of lithium ions at the anode through the electrolyte (migrat
e) and let it enter the carbon-based anode material (intercal
ate). The battery then begins to discharge (power) in the normal manner.

[0003] Graphite-like carbon is generally preferred as the anode material because the graphite composition has an acceptable cycling capacity and good reversible capacity, especially in the initial charge discharge cycle. . For this reason, graphite is usually used, but other carbon-based materials with better reversibility also exist. One of them is hard carbon. Although this material is very good in cycling properties, it has a problem that the initial irreversibility is relatively large.

[0004]

Therefore, the secondary battery according to the present invention can be used as a part of a negative electrode in addition to an alkali metal intercalate and a de-intercalate material such as a carbonaceous anode material. `` Sacrificial part '' of alkali metal (sac
rificial piece). In the case of hard carbon, a lithium metal piece is desirable as the alkali metal constituting the "sacrifice" portion, and is adjusted to a size suitable for compensating for the initial irreversibility of the anode material. After activating the battery with the electrolyte, the lithium metal automatically intercalates into the hard carbon anode material. By such means, the "sacrificial" lithium metal compensates for the generally unavoidable irreversible capacity of hard carbon. Thus, the superior cycling longevity of hard carbon is exploited, resulting in a longer service life than known in conventional secondary batteries having only graphite anode material.

[0005]

SUMMARY OF THE INVENTION Accordingly, one of the objects of the present invention is to improve the cycling performance of lithium ion batteries by providing a new concept in negative electrode design. Still another object of the present invention is to provide a battery design that can improve the capacity and utilization efficiency of a lithium-containing secondary battery. These and other objects of the present invention will become more apparent to those skilled in the art by reference to the following description.

[0006]

DETAILED DESCRIPTION OF THE INVENTION An electrochemical cell according to the present invention comprises:
It is a secondary rechargeable chemical battery. The battery comprises an anode active metal selected from the group IA, IIA and IIIB of the Periodic Table of the Elements, including lithium, sodium, potassium and the like.

In conventional secondary electrochemical systems, the anode or anode is preferably composed of an anode material capable of intercalating and de-intercalating an anode active material such as lithium alkali metal. Typically, the anode material of the negative electrode is made of various forms of carbon that can reversibly retain lithium species (for example, coke, graphite, acetylene black, carbon black, glass carbon, and the like). In conventional secondary batteries, graphite is particularly preferred. Also, "Hairy carbon"
Due to its relatively high lithium retention capacity, it is another material that is particularly preferred as a conventional material. "Hairy carbon" is described in Takeuchi et al., U.S. Pat. No. 5,443,928, assigned to the assignee of the present invention.

However, the graphite form composition of carbon does not have high reversibility comparable to the reversible capacity of hard carbon. Hard carbon, defined as a non-graphitic carbon material, has a reversibility of 2 to 4 times the reversible capacity of graphite. Hard carbon is
Typically, a suitable organic cursor
It is produced by firing at a temperature of 700 ° C to 1,200 ° C. Hard carbon typically exhibits very good cycling properties and high reversible capacitance. At present, that is, graphite is theoretically limited to a capacity of 372 mAh / g, but hard carbon can provide a capacity of 400 mAh / g or more. This means that a secondary battery constructed using hard carbon as the anode material has 2 to 4 times more charge discharge or cyclability than a secondary battery constructed using the graphite former as the anode material. are doing. The improvement in cycle life is based on the dimensional stability of hard carbon during intercalation and de-intercalation of lithium. This is because a secondary battery constructed using hard carbon as an anode material has , Potentially having a higher capacity than secondary batteries constructed using graphite formers as the anode material.

[0009] On the other hand, the main reason that hard carbon is not used more frequently in secondary batteries is that the irreversible capacity in the initial cycle is larger when compared to graphite. This irreversible capacity will in turn reduce the capacity of the battery and must be compensated for by adding a cathode active material to the battery.

For this reason, the negative electrode of the secondary battery of the present invention has a double screen structure having a piece of “sacrificial portion” sandwiched between two current collectors made of an alkali metal, preferably lithium. Is built as A substance capable of intercalating and de-intercalating a carbon-based material or an alkali metal is in contact with at least one, preferably both, current collectors on opposite sides. The role of the "sacrifice" alkali metal is to compensate the graphite for the irreversible capacity of intercalate and de-intercalate substances found, for example, in hard carbon. One embodiment of the negative electrode of the present invention has the following configuration. Hard carbon / Current collector /
Lithium / current collector / hard carbon

In such a dual collector electrode design of the present invention, the amount of lithium metal is adjusted in order to accurately compensate for the irreversible capacity of hard carbon. When the battery is activated by the ion conductive electrolyte, the alkali metal moves into the hard carbon, and the alkali metal is completely consumed. Lithium metal is preferably sandwiched between the two current collectors so that the absence of the alkali metal in the battery does not result in the loss of the desired safety and cycling characteristics of the intercalated anode and anode. Sandwiched. Further, the negative electrode of this embodiment in which the current collector is sandwiched between two hard carbon structures is a conventional carbon-based negative electrode in contact with only one current collector. The energy density is much higher in volume and / or weight than in the other.

Regardless of the nature or composition of the carbonaceous material of the anode material, fibers are particularly beneficial. The mechanical properties of the fiber are very good, and a robust electrode structure can be constructed that can be continuously degraded during repeated charge and discharge cycles. Further, since the surface area of the carbon fiber is large, charge discharge can be performed at high speed.

The carbon-based material of the negative electrode for a secondary battery according to this embodiment is formed by mixing about 90 to 97% by weight of an anode material, preferably hard carbon, and about 3 to 10% by weight of a binder. You. This binder includes polytetrafluoroethylene (PTEE), polyvinylidene fluoride (PVDF), polyethylene tetrafluoroethylene (ETFE), polyamide,
Fluorine resin binders such as polyimides and mixtures thereof are preferred.

The negative electrode mixed material is, for example, a high alloy ferritic stainless steel containing copper, stainless steel, titanium, tantalum, platinum, gold, aluminum, nickel, cobalt nickel alloy, molybdenum and chromium,
In addition, the present invention is applied to a current collector comprising a nickel-containing, chromium-containing, molybdenum-containing alloy foil or a screen by a casting method, a pressing method, a rolling method, or another contact method.

[0015] Another type of anode material useful in the present invention is a metal that can reversibly alloy with alkali metals. Such metals include Sn, Si, Al, Pb, Zn and Ag
, But is not limited to this. These alloyed metals have very good reversible capacities, but their cycling properties are poor due to large-scale dimensional changes during the alloying process. One method used to solve this problem is to suspend those nano-sized particles in a matrix of inert material. This inert material is typically made by reducing the oxide of the alloying metal during the first cycle. Examples of oxides, SnO, SnO _2, SiO and _{SnO (B 2 O 3) x} (P 2 O 5) y
, But is not limited to this. These oxides exhibit good cycling properties and high reversible capacities, but large amounts of alkali metal are consumed during the first charge during reduction of the metal oxide. For this reason, in conventional secondary chemistry (batteries), additional cathode active material must be incorporated into the battery to compensate for this reduction, which results in a reduction in the capacity of the battery.

Therefore, in another preferred embodiment of the present invention, an alkali metal piece is arranged between the metal oxide anode materials. As for the amount of the alkali metal, an amount that accurately compensates for the reduction of the metal oxide is selected. Next, when the battery is activated by the ion-conductive electrolyte, the alkali metal moves into the anode material, and the alkali metal is completely consumed. As before, the absence of alkali metals in the battery does not result in the loss of the desired safety and cycling properties of the anode material,
As a result, a battery capacity that can clear the current situation in this field can be secured.

In another preferred embodiment of the present invention, an active material that is typically used as a cathode active material for a primary battery, but is not normally used in a conventional secondary battery, is utilized. In the current state of the rechargeable battery field, an anode is typically used as an ion source of alkali metal ions, which hinders the use of a metal-containing cathode active material that does not contain alkali metal ions. Examples of such metal-containing materials include V ₂ O ₂ , SVO, CSVO, Mn
O ₂ , TiS ₂ , CuO ₂ , Cu ₂ S, FeS, FeS ₂ , CF _x , Ag ₂ O, Ag
₂ O ₂ , CuF, Ag ₂ CrO ₄ , copper oxide, copper vanadium oxide and mixtures thereof. When these active materials are used in the anode of a secondary battery, the presence of an alkali metal anode or a pre-metallized anode material (the most desirable material is carbon) is usually required. As discussed above, these materials are undesirable because of their poor cyclability and safety. Pre-metallized carbon materials are known in the art, but are not commercially available because reliable manufacturing methods have not been established.

In the present invention, the alkali metal piece is as described above,
Typically used in conjunction with one or more metal-containing materials used as cathode active materials in primary batteries. That is, in the present invention, the alkali metal piece serves as an ion source of an alkali metal ion, and is disposed between two layers of one or more kinds of the metal-containing metals serving as an anode material here, in a sandwich manner. Has become. As for the amount of the alkali metal, an amount that accurately compensates the reversible capacity of the anode material is selected. When the battery is activated by the ionic conductive electrolyte, the alkali metal migrates into the anode material and the alkali metal is completely consumed, thereby ensuring the desired safety and cycling characteristics of the anode material.

Here, any of the materials described above as useful anode materials in the negative electrode of the present invention and which form an acceptable electrochemical potential for the anode material can be used as the active material of the anode. is there. As described above, since these materials are not lithiated, they are not used as typical cathode active materials in secondary batteries. As an illustrative combination, graphite / Li is used for the negative electrode and V ₂ O ₅ or SVO is used for the positive electrode.

When the above-mentioned carbon-based anode material is used,
The alloyed anode metal as well as the metal-containing anode material is formed in the sandwich electrode body by mixing with one or more of the above-described binders for incorporation in an electrochemical cell, and more preferably, Approximately 10% by weight of a conductive diluent is added to the mixture to improve conductivity. Suitable materials for this purpose include acetylene black, carbon black and / or graphite or metal powders such as powdered nickel, aluminum, titanium and powdered stainless steel. Thus, a preferred anode material mixture comprises about 1 to 5% by weight powdered fluoropolymer binder and about 1 to 5% by weight conductive diluent.
5%, and about 90-98% of the anode material.

Thus, one illustrative negative electrode has an anode material that is shorted to the alkali metal anode active material by being joined in parallel via a current collector. The following configuration is an example. First anode material / current collector / alkali metal / current collector / second anode material, wherein the first anode material and the second anode material are either the same material or different materials.

In another embodiment of the present invention, the alkali metal is sandwiched between the anode materials, and the anode material is short-circuited to the alkali metal by direct contact. The configuration of this negative electrode is as follows. First anode material / current collector / second anode material / alkali metal / third anode material / current collector / fourth anode material Here, the first, second, third and fourth anode materials are the same material. Or made from any of the different materials.

The configuration of the third exemplary embodiment of the present invention is as follows. Anode material / current collector / alkali metal, where the anode material faces the anode.

As a further preferred embodiment, the following negative electrode configuration is included. Hard carbon / current collector / lithium / current collector / hard carbon or anode material / current collector / lithium / current collector / anode material, where the anode material is SnO 2, SnO ₂ , SiO ₂ , Sn
O (B ₂ O ₃ ) _x (P ₂ O ₅ ) _y , V ₂ O ₅ , SVO, CSVO, MnO ₂ , TiS ₂ , C
uO ₂ , Cu ₂ S, FeS, FeS ₂ , CF _x , Ag ₂ O, Ag ₂ O ₂ , CuF
, Ag ₂ CrO ₄ , copper oxide, copper vanadium oxide and mixtures thereof. Alternatively, a carbon-based material / current collector / lithium / current collector / carbon-based material or graphite / current collector / graphite / lithium / graphite / current collector / graphite.

In the case of a secondary battery, the reaction at the anode involves the conversion of ions traveling from the negative electrode to the anode into atomic or molecular forms. The anode is preferably composed of lithiated oxides, sulfides, selenides, and tellurides of metals such as vanadium, titanium, chromium, copper, molybdenum, niobium, iron, nickel, cobalt and manganese. Preferred lithiated oxides include Li _x Ti ₅ O ₁₂ x = 4 to 7), Li _3-x M _x N (M = Co or N
i, x = 0.1-0.6), LiNiO ₂ , LiMn ₂ O ₄ , LiMnO ₂ , LiV
₂ O ₅ , LiCoO ₂ , LiCo _0.92 Sn _0.08 O ₂ and LiCo _1-x Ni _x O ₂
Is included. SVO, CSVO, Ag ₂ O, Ag ₂ O ₂ , CuF ₂ , A
_{g 2 CrO 4, MnO 2,} V 2 O 5, TiS 2, Cu 2 S, FeS, FeS 2, copper oxide, alkali metal intercalated and de such as copper vanadium oxide and mixtures thereof - also intercalated materials, Further, it is useful as a cathode active material.

In order to charge such a secondary battery, by applying an electric potential to the battery from the outside, the lithium ions constituting the anode are converted into a carbon-based anode material of the anode or lithium intercalate and de-intercalate. It is intercalated into the anode material and charged. Due to the applied charging potential, lithium ions are drawn from the cathode active material through the electrolyte and into the anode material, saturating the anode material. For carbon, Li _x C ₆
The x value results in a range of 0.1 to 1.0. As a result, the electric charge is stored in the battery, and the battery is discharged in a usual manner.

The cathode active material is formed in the anode by mixing with one or more of the binders described above and a conductive diluent. Preferred cathode active mixtures include about 1-5% by weight powdered fluoropolymer binder, about 1-5% by weight conductive diluent, and about 90-98% cathode active material. Things.

When incorporating the anode in an electrochemical cell according to the present invention, the cathode active formulation is rolled onto a suitable current collector made from any one of the materials described above suitable for the negative electrode, It can be realized by stretching or pressing. The preferred current collector material is aluminum, and the anode made as described above may be in the form of one or more plates that are functionally associated with one or more negative plates, or a "jellyroll". It can be a strip type in which a corresponding negative electrode strip having such a structure is wound.

To avoid an internal short circuit condition, the negative electrode is separated from the anode by a suitable separator. The separator is composed of an electrically insulating material, which is chemically inert with the anode active material and the cathode active material, both of which are chemically inert to the electrolyte and also insoluble. Further, the material of the separator has sufficient porosity to generate a flow through the electrolyte during the electrochemical reaction of the battery. Illustrative materials for the separator include fabrics woven from fluoropolymeric fibers including polyvinylidene fluoride, polyethylene tetrafluoroethylene, and polyethylene chlorotrifluoroethylene (either used alone or fluoropolymeric fibers). Laminated with microporous film), non-woven glass, polypropylene, polyethylene, glass fiber material, ceramic, polytetrafluoroethylene membrane commercially available under the name ZITEX (Chemplast Inc.), CELGAR
A polypropylene membrane commercially available under the name of D (Celanese Plastic Company, Inc.) and DEXIGLAS (CH Dext
er, Div., Dexter Corp.).

The electrochemical cell according to the present invention further includes a non-aqueous ionic conductive electrolyte which acts as a transfer medium between the negative electrode and the positive electrode during the electrochemical reaction of the cell. Suitable electrolytes have an inorganic ionic conductive salt dissolved in a non-aqueous solvent, and more preferably, the electrolyte includes an aprotic organic solvent composed of a low viscosity solvent and a high dielectric constant solvent. Includes ionized alkali metal salts that dissolve in the mixture. The inorganic ion conductive salt serves as a solvent for intercalating anodic ions or promoting ion transfer for causing a reaction with the cathode active material. The ion forming the alkali metal salt is preferably an ion similar to the alkali metal forming the anode active material.

In the case of an anode active material composed of lithium, the alkali metal salt of the electrolyte is a salt having lithium as a base. The beneficial known lithium salt as a solvent for causing the transport between the alkali metal ions and the negative electrode and the _{anode, LiPF 6, LiBF 4, LiAsF} 6, LiSbF 6, LiClO 4, LiO 2,
LiAlCl ₄ , LiGaCl ₄ , LiC (SO ₂ CF ₃ ) ₃ , LiN (SO ₂ CF ₃ ) ₂ , Li
SCN, LiO ₃ SCF ₃ , LiC ₆ F ₅ SO ₃ , LiO ₂ CCF ₃ , LiSO ₆ F, LiB
There are (C ₆ H ₅ ) ₄ , LiCF ₃ SO ₃ and mixtures thereof.

The low viscosity solvents useful in the present invention include esters, linear ethers, cyclic ethers, tetrahydrofuran (THF), methyl acetate (MA), diglyme, triglyme, tetraglyme, dimethyl carbonate (DMC), 1,2 -Dimethoxyethane (DME), 1,2-diethoxyethane (DEE), 1-ethoxy, 2-methoxyethane
(EME), ethyl methyl carbonate (EMC), methyl propyl carbonate, ethyl propyl carbonate, diethyl carbonate (DEC), dipropyl carbonate and mixtures thereof, and high dielectric constant solvents include polypropylene carbonate (PC), ethylene Carbonate (EC), butylene carbonate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide,
There are cyclic carbonates, cyclic esters and cyclic amides such as γ-valerolactone, γ-butyrolactone (GBL), N-methyl-pyrrololidinone (NMP) and mixtures thereof.

A preferred electrolyte for the secondary battery of the present invention is an EC: DMC: EMC: DEC solvent mixture. The most preferred solvent mixing ratios for the various carbonate solvents are about 20% to about 50% EC and about 12% to 75% DMC.
%, EMC is about 5% to 45%, and DEC is about 3% to 45%.
A preferred battery activation electrolyte composition applicable to the present invention is to balance the DMC: EMC: DEC ratio. This is important in maintaining constant and reliable cycling characteristics. In a charged battery, the presence of a low potential (anode) material causes the presence of DM in the presence of lithiated graphite (LiC _{6 to} 0.01 V vs. Li / Li ⁺ ).
C: DEC unbalanced mixtures are known to result in the formation of substantial amounts of EMC. Varying concentrations of DMC, DEC and EMC will alter the cycling characteristics and temperature rating of the battery. Such unpredictability is not preferred. This phenomenon was observed in US patent application Ser. No. 09/66, filed Sep. 26, 2000 and assigned to the present applicant.
It is detailed in issue 9,936. The electrolyte containing the four-carbonate mixture of the present invention has a freezing point lower than -50 ° C, and the cycling characteristics (operation) at room temperature of the lithium ion secondary battery activated by such a mixture are very good. The discharge output and charge / discharge cycling characteristics at -40 ° C or lower are also good.

The secondary battery assembly described above is preferably formed as a wound element configuration. That is, the negative electrode, the positive electrode, and the separator that are manufactured are all configured in a “jelly roll” type, or the negative electrode is disposed outside the roll and electrically connected to the battery case in the case negative electrode configuration. Wound element ce
ll stack) system. By using appropriate upper and lower insulators, the laminated winding element section is:
It can be placed in a metal case of appropriate dimensions and size. This metal case can use materials such as stainless steel, mild steel, nickel-plated mild steel, titanium, tantalum or aluminum, as long as the metal material has compatibility with other battery components, but is not limited to these. Absent.

The battery header is comprised of a metal disk-shaped body having a first opening that accommodates a seal / terminal pin feedthrough between glass and metal, and a second opening for electrolyte filling. Opening. Glass used is CABAL12, TA23, FUSITE425 or FUSITE435
It is a corrosion-resistant type containing about 50% by weight of silicon such as. The anode terminal pin feedthrough is preferably made of titanium, but molybdenum, aluminum, nickel alloy or stainless steel can also be used. Battery headers are typically made from materials similar to those of the case. The anode terminal pin is held by the header via a seal between the glass and the metal, and is then welded and fixed to a case accommodating the laminated electrode. The battery is then filled with the above-mentioned electrolyte solution, and the filled hole is hermetically sealed without being limited to this method, for example, by a method of tightly welding a stainless steel ball or the like.

The above assembly is an example of an assembly of a case and a negative electrode battery, and is an example of a preferred secondary battery structure of the present invention. As is well known to those skilled in the art, such secondary electrochemical systems can also be constructed in case and anode configurations.

The above embodiments can be variously modified without departing from the spirit of the present invention and the scope shown in the claims, and this will be apparent to those skilled in the art.

────────────────────────────────────────────────── ───Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01M 4/62 H01M 4/62 Z 4/66 4/66 A (72) Inventor Robert S., Rubino United States of America, New York 14221, Williamsville, Bauman Road 97 (72) Inventor Esther S., Takeuchi 14051, New York, United States, East Amherst, Saint-Raphael Court 38 F-term (reference) 5H017 AA03 AS10 BB12 DD00 EE01 HH05 5H029 AJ03 AJ05 AK02 AK03 AK05 AL02 AL03 AL04 AL06 AL12 AL18 AM02 AM03 AM04 AM05 AM07 BJ12 BJ14 CJ05 CJ07 DJ07 DJ08 EJ01 EJ04 EJ12 HJ12 5H050 AA07 AA08 BA15 CA02 CA07 CA11 CB02 CB03 CB05 CB07 CB12 CB30 DA03 DA06 DA07 FA08 DA06 DA07 FA08

Claims (39)

[Claims] 1. An anode made of an anode material short-circuited by an anode active material; b) an anode made of a cathode active material; and c) a non-aqueous electrolyte for activating the anode and the anode. An electrochemical battery, characterized in that: 2. The method according to claim 1, wherein the anode active material is one of I in the periodic table of elements.
2. The electrochemical cell according to claim 1, wherein the cell is selected from the group A, IIA and IIB. 3. The anode material is a carbon-based material, SnO 2, Sn
O_Two, SiO 2, SnO (B_TwoO_Three)_X (P _TwoO_Five)_y , V_TwoO_Five, SVO, CSVO,
MnO_Two, TiS_Two, CuO_Two, Cu_TwoS, FeS, FeS_Two, CF_x , Ag_TwoO, Ag
_TwoO_Two , CuF, Ag_TwoCrO_Four , Copper oxide, copper vanadium oxide,
Selected from the group consisting of
2. The electrochemical cell according to claim 1, wherein: 4. The electrochemical cell according to claim 3, wherein the carbon-based material is selected from the group consisting of coke, graphite, acetylene black, carbon black, glass carbon, hairy carbon, hard carbon and mixtures thereof. . 5. A negative electrode comprising a first anode material / current collector / alkali metal / current collector / second anode material, wherein the first and second anode materials have the same or different compositions, The electrochemical cell according to claim 1, wherein the alkali metal can be intercalated and de-intercalated. 6. The negative electrode comprises a first anode material / current collector / second anode material / alkali metal / third anode material / current collector /
A structure comprising a fourth anode material, wherein the first, second, third and fourth anode materials are the same or different materials and are capable of intercalating and de-intercalating an alkali metal. The electrochemical cell according to claim 1, wherein 7. The negative electrode has a structure of anode material / current collector / alkali metal, wherein the anode material is capable of intercalating and de-intercalating the alkali metal. The electrochemical cell according to claim 1. 8. The electrochemical cell according to claim 5, wherein the anode material faces the anode. 9. The anode material is hard carbon,
The negative electrode is hard carbon / current collector / lithium / current collector /
The electrochemical cell according to claim 1, wherein the electrochemical cell has a configuration of hard carbon. 10. The method according to claim 1, wherein the anode material is hard carbon, the negative electrode has a structure of hard carbon / current collector / lithium, and the hard carbon faces the anode. Electrochemical battery. 11. The anode material is hard carbon, and the negative electrode has a structure of hard carbon / current collector / hard carbon / lithium / hard carbon / current collector / hard carbon. Item 2. An electrochemical cell according to Item 1. 12. The electrochemical device according to claim 1, wherein the anode material is a carbonaceous material, and the negative electrode has a structure of carbonaceous material / current collector / lithium / current collector / carbonaceous material. Battery. 13. The method according to claim 13, wherein the cathode active material is Li_x Ti_FiveO₁₂(x = 4 ~
7), Li_3-X M_X N (M = Co or Ni, x = 0.1-0.6), LiNi
O_Two, LiMn_TwoO_Four , LiMnO_Two, LiV_TwoO_Five, LiCoO_Two, LiCo_0.92Sn
_0.08O_Two, LiCo_1-X Ni_X O_Two, SVO, CSVO, V_TwoO_Five, MnO_Two, Cu
O_Two, TiS_Two, Cu_TwoS, FeS, FeS_Two, Copper oxide, vanadium oxide
Copper, CF_X , Ag_TwoO, Ag_TwoO_Two , CuF, Ag_TwoCrO_Four And that
Specially selected from the group consisting of mixtures.
2. The electrochemical cell according to claim 1, wherein: 14. The electrochemical cell according to claim 1, wherein the anode comprises an inactive material selected from a binder material and a conductive additive. 15. The electrochemical cell according to claim 14, wherein the binder material is a fluororesin powder. 16. The method according to claim 14, wherein the conductive additive is selected from the group consisting of carbon, graphite powder, acetylene black, titanium powder, aluminum powder, nickel powder, stainless steel powder and mixtures thereof. Electrochemical battery. 17. An anode comprising: a) a cathode active material; and b) an anode material and an alkali metal, wherein the first and second major sides of the alkali metal correspond to the first and second major sides. Separated by at least one current collector in contact with at least one of the anode material, the anode material is in contact with the at least one current collector on the opposite side of the alkali metal, faces the anode, and the anode material is an alkali metal. An electrochemical cell comprising: a negative electrode adapted to intercalate and de-intercalate; and c) a non-aqueous electrolyte for activating the negative electrode and the positive electrode. 18. The negative electrode including the first and second current collectors,
A first anode material / first current collector / alkali metal / second current collector / second anode material, wherein the first and second anode materials are the same or different materials and the alkali metal is intercalated. 18. The electrochemical cell according to claim 17, wherein the electrochemical cell is capable of being de-intercalated. 19. A structure in which the anode material is a carbon-based material, the negative electrode includes first and second current collectors, and the following structure: carbon-based material / first current collector / lithium / second current collector / carbon-based material The electrochemical cell according to claim 17, wherein: 20. The anode material is hard carbon,
18. The electric device according to claim 17, wherein the negative electrode includes the first and second current collectors, and has a configuration of hard carbon / first current collector / lithium / second current collector / hard carbon. Chemical battery. 21. The current collector is made of copper, stainless steel,
It is selected from the group consisting of titanium, tantalum, platinum, gold, aluminum, cobalt nickel alloy, high alloy ferritic stainless steel containing molybdenum and chromium, and alloy containing nickel, chromium, and molybdenum. Claim 17
An electrochemical battery according to claim 1. 22. The electrolyte, wherein the electrolyte is an ester, a linear ether,
18. The method according to claim 17, comprising a first solvent selected from a cyclic ether, a dialkyl carbonate and a mixture thereof, and a second solvent selected from a cyclic carbonate, a cyclic ester, a cyclic amide and a mixture thereof. Electrochemical battery. 23. The first solvent is tetrahydrofuran (TH
F), methyl acetate (MA), diglyme, triglyme,
Tetraglyme, dimethyl carbonate (DMC), 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE)
1-ethoxy, 2-methoxyethane (EME), ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, diethyl carbonate, dipropyl carbonate and mixtures thereof, wherein the second solvent is propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, γ-valerolactone, γ-butyrolactone (GBL), N-methyl-pyrrololidinone (NMP) and mixtures thereof 23. The electrochemical cell according to claim 22, wherein the cell is selected from the group consisting of: 24. An electrolyte comprising: LiPF ₆ , LiBF ₄ , LiAsF ₆ ,
LiSbF ₆ , LiClO ₄ , LiO ₂ , LiAlCl ₄ , LiGaCl ₄ , LiC (SO ₂ C
F ₃ ) ₃ , LiN (SO ₂ CF ₃ ) ₂ , LiSCN, LiO ₃ SCF ₃ , LiC ₆ F ₅ SO ₃ ,
_{LiO 2 CCF 3, LiSO 6 F} , LiB (C 6 H 5) 4, LiCF 3 SO 3 and electrical of claim 17, characterized in that it comprises a lithium salt selected from the group consisting of a mixture thereof Chemical battery. 25. The electrolyte, characterized in that the volume percentage of propylene carbonate and 1,2-dimethoxyethane is LiAsF ₆ or LiPF ₆ in 0.8M~1.5M dissolved in a mixture of 50:50 claims Item 18. An electrochemical cell according to Item 17. 26. An anode comprising a cathode active material; and b) an anode material in contact with one side of the current collector, wherein the alkali metal is located on the other side of the current collector. A negative electrode comprising an anode material, wherein the material faces the anode and the alkali metal can be intercalated and de-intercalated; and c) a non-aqueous electrolyte which activates the negative electrode and the anode. An electrochemical battery, comprising: 27. The anode material is hard carbon,
27. The electrochemical cell according to claim 26, wherein the configuration of the negative electrode is hard carbon / current collector / lithium, and the hard carbon faces the anode. 28. The method according to claim 26, wherein the anode material is a carbon-based material, the structure of the negative electrode is carbon-based material / current collector / lithium, and the carbon-based material faces the anode. Electrochemical battery. 29. The anode material is composed of SnO ₂ , SnO ₂ , SiO ₂ , Sn
O (B ₂ O ₃ ) _x (P ₂ O ₅ ) _y , carbon-based material, SVO, CSVO, V ₂ O ₅ ,
MnO ₂ , CuO ₂ , TiS ₂ , Cu ₂ S, FeS, FeS ₂ , copper oxide, copper vanadium oxide, CF _X , Ag ₂ O, Ag ₂ O ₂ , CuF, Ag ₂ CrO ₄ and mixtures thereof 27. The electrochemical cell according to claim 26, wherein the cell is selected from a group. 30. A negative electrode made of an alkali metal sandwiched between a first current collector and a second current collector, comprising: a) an anode made of a cathode active material; and an anode material. _{but, SnO, SnO 2, SiO,} SnO (B 2 O 3) x (P 2 0 5) y, carbon-based _{materials, V 2 O 5, SVO,} CSVO, MnO 2, TiS 2, CuO 2, Cu 2 S ,
FeS, FeS ₂ , CF _x , Ag ₂ O, Ag ₂ O ₂ , CuF, Ag ₂ CrO ₄ , copper oxide, vanadium copper oxide and mixtures thereof, selected from the group consisting of alkali metals An electrochemical device comprising: a negative electrode in contact with at least one of the first and second current collectors on the opposite side and facing the anode; and c) a non-aqueous electrolyte activating the negative electrode and the anode. Battery. 31. A method for providing an electrochemical cell, comprising: a) providing an anode comprised of a cathode active material; and b) providing an anode comprised of an alkali metal shorted by an anode material. And c) activating the negative electrode and the positive electrode with the non-aqueous electrolyte. 32. A method comprising providing a negative electrode having a structure of a first anode material / current collector / alkali metal / current collector / second anode material, wherein the first and second materials are made of the same or different materials. 32. The method of claim 31, wherein the anode material is capable of intercalating and de-intercalating an alkali metal. 33. A method comprising providing a negative electrode having the following structure: a first anode material / current collector / second anode material / alkali metal / third anode material / current collector / fourth anode material. 32. The method of claim 31, wherein the, second, third and fourth anode materials are the same or different materials and are capable of intercalating and de-intercalating alkali metals. 34. A method comprising providing a negative electrode having a structure of anode material / current collector / alkali metal, wherein the anode material is capable of intercalating and de-intercalating an alkali metal, and 32. The method of claim 31, wherein the method is adapted to face to face. 35. The method of claim 31, including providing a hard carbon anode material, wherein the negative electrode configuration is hard carbon / current collector / lithium / current collector / hard carbon. 36. The method according to claim 36, further comprising the step of providing an anode material made of a carbonaceous material, wherein the structure of the negative electrode is carbonaceous material / current collector / lithium, and the carbonaceous material faces the anode. Item 34. The method according to Item 31. 37. A process for providing an anode material comprising a carbonaceous material, wherein the structure of the negative electrode is carbonaceous material / current collector / lithium / current collector / carbonaceous material. Item 34. The method according to Item 31. 38. The anode material is made of SnO 2, SnO 2_Two, SiO, Sn
O (B_TwoO_Three)_x (P_TwoO_Five)_y , Carbonaceous material, V_TwoO_Five, SVO, CSVO,
MnO_Two, TiS_Two, CuO_Two, Cu_TwoS, FeS, FeS_Two, CF_X , Ag _TwoO, Ag
_TwoO_Two , CuF, Ag_TwoCrO_Four , Copper oxide, copper vanadium oxide and
Selected from the group consisting of
32. The method of claim 31, wherein: 39. The method according to claim 38, wherein the carbon-based material is selected from the group consisting of coke, graphite, acetylene black, carbon black, glass carbon, hairy carbon, hard carbon and mixtures thereof. Method.