EP1512187A1 - Lithium based electrochemical devices having a ceramic separator glued therein by an ion conductive adhesive - Google Patents

Lithium based electrochemical devices having a ceramic separator glued therein by an ion conductive adhesive

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Publication number
EP1512187A1
EP1512187A1 EP02807507A EP02807507A EP1512187A1 EP 1512187 A1 EP1512187 A1 EP 1512187A1 EP 02807507 A EP02807507 A EP 02807507A EP 02807507 A EP02807507 A EP 02807507A EP 1512187 A1 EP1512187 A1 EP 1512187A1
Authority
EP
European Patent Office
Prior art keywords
electrochemical device
separator
range
percentage weight
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02807507A
Other languages
German (de)
French (fr)
Inventor
Joseph B. Kejha
Novis W. Smith
Joel R. Mccloskey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP1512187A1 publication Critical patent/EP1512187A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/02—Diaphragms; Separators
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0436—Small-sized flat cells or batteries for portable equipment
    • H01M10/044—Small-sized flat cells or batteries for portable equipment with bipolar electrodes
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H01M4/745—Expanded metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to lithium based electrochemical devices
  • lithium-ion polymer batteries use plasticized polymeric solid separators sandwiched between plasticized electrodes, and laminated to the electrodes
  • plasticizer must be extracted by a flammable solvent. The cell, after
  • plasticizer extraction is activated (soaked) by a non-aqueous flammable
  • the separator in the welding step, the separator must be relatively thick
  • the separator contain a binder which hold their particle materials together.
  • the cell is held together by a housing, or the separator is coated onto a
  • cathode or anode active layer is solidified by solvent evaporation
  • the cell is then fused together by pressing and heating to melt the binder or
  • the cell also has solid metal foil
  • separator only, not a bonded cell or device and the separator is limited to a
  • lithium-ion cells for example lithium-ion cells, capacitors and the like can be made with
  • a single cell structure which includes a porous first electrode with a binder
  • a porous second electrode with a binder which may be a
  • ionically conductive polymeric adhesive layer may be solidified by solvent
  • the principal object of the invention is to provide electrochemical
  • devices which preferably include a porous first electrode with a binder, a
  • porous ceramic separator with an ionically conductive adhesive layer, a
  • a further object of the invention is to provide electrochemical
  • a further object of the invention is to provide electrochemical
  • a further object of the invention is to provide electrochemical
  • a further object of the invention is to provide electrochemical
  • FIG. 1 is a side elevational and sectional view of an electrochemical
  • FIG. 2 is a top elevational plan view of the device of FIG. 1.
  • an electrochemical device 10 which in this instance is a lithium ion
  • the cell 10 includes a porous first electrode 11, which may be an
  • a thin porous ceramic separator 14 which contains a binder (to be described), and electrically insulating particles
  • electrode 17 is provided with a binder, which may be a cathode active
  • microgrid current collector 19 which has the cathode active surface 20
  • the second electrode 17 may be
  • the adhesive layer 16 may be solidified by solvent evaporation
  • collectors 12 and 19 are porous, the solvent which may be contained in the
  • adhesive layer 16 is easily evaporated resulting in improved adhesion and
  • the cell K) components may also be used, such as 1 mole Li PF 6 in ethylene
  • the cell 10 after activation is placed into a moisture proof enclosure
  • Both the electrode coatings may be well known slurries as used in
  • microgrids 12, and 19 by a doctor blade, slot coating or reverse roll coating.
  • a support release film (not shown) is provided under the grids 12 and 19
  • the binder of the electrodes 11 and 17 and separator 14 may be of
  • the separator 14 binder may be polyvinylidene (PVDF)
  • the binder of the electrodes 11 and 17 may be polyvinyl
  • the NMP component is useful in a range of 40 to 60 %
  • the PVDF component is useful in a range of 2 to
  • the alpha alumina component is useful in a
  • the H 2 0 component is useful in a range of 40 to 60%, by percentage
  • the PVOH component is useful in a range of 2 to 10% by
  • the fluoride component is usefiil in a range of 25 to 75% by percentage weight.
  • Other electrically insulating particles are also present.
  • the DME component is useful in a range of 40 to 95% by
  • the PVDF/HFP component is useful in a range of 5 to
  • the electrolyte is useful in a range of 10 to 20% by percentage weight, and the electrolyte is useful in a range of 10 to 20% by percentage weight, and the electrolyte is useful in a range of 10 to 20% by percentage weight, and the electrolyte is useful in a range of 10 to 20% by percentage weight, and the electrolyte is useful in a range of 10 to 20% by percentage weight, and the electrolyte is useful in a range of 10 to
  • PVDF homopolymer (Aldrich) 30g
  • the PVDF component is useful in a range of 5 to 50% by percentage weight
  • electrolyte component is useful in a range of 50 to 95% by percentage
  • lithium salts such as Lithium Methide, Lithium
  • Lithium Beti are also suitable.
  • the lithium salt components are useful in a range of 0.5M to 3M,
  • ethylene carbonate (EC) component is useful in a range of 40 to 90% by
  • the propylene carbonate (PC) component is useful in a
  • (GBL) component is useful in a range of 5 to 70% by percentage weight.
  • the invention is also easier due to lack of plasticizer, extraction step, and
  • the separator layer may be 1 mil or thinner, and the adhesive
  • layer may be 1 mil or thinner.
  • the cell assembly should be done under inert atmospheric conditions, and

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Cell Separators (AREA)
  • Primary Cells (AREA)

Abstract

Lithium based electrochemical devices which contain at least two porous electrodes, which include expanded metal microgrids coated with active materials, with a porous ceramic separator therebetween in adherent contact with one electrode, and an ionically conductive organic adhesive on said separator in adherent contact with said second electrode. A non-aqueous electrolyte is soaked into the electrodes and the separator with the device contained in an enclosure with two external terminals.

Description

JOSEPH B. KEJHA
W. NOVIS SMITH
JOEL R. McCLOSKEY
LITHIUM BASED ELECTROCHEMICAL DEVICES
HAVING A CERAMIC SEPARATOR GLUED THEREIN BY AN
ION CONDUCTIVE ADHESIVE.
BACKGROUND OF THE INVENTION FIELD OF THE INVENTION
This invention relates to lithium based electrochemical devices
which have a porous first electrode with a binder, a porous ceramic
separator with a binder in bonding contact with the first electrode, a thin
layer of ionically conductive organic adhesive on the separator, a porous
second electrode with a binder, in contact with the polymeric adhesive
layer, and a non-aqueous electrolyte, all contained within a moisture proof
outer enclosure with external terminals.
DESCRIPTION OF THE PRIOR ART
Prior art lithium based electrochemical devices, and for example
lithium-ion polymer batteries use plasticized polymeric solid separators sandwiched between plasticized electrodes, and laminated to the electrodes
by heat welding, to make the cell assembly, as disclosed in U.S. Patent No.
5,587,253 of Gozdz et. al. To make the cell porous for activation, the
plasticizer must be extracted by a flammable solvent. The cell, after
plasticizer extraction, is activated (soaked) by a non-aqueous flammable
electrolyte, and sealed into a housing or pouch. Due to the softness of the
separator material in the welding step, the separator must be relatively thick
to prevent shorts, which decreases the energy density of the cell. If a
thinner separator is used, the production yield is poor due to shorts. While
the Gozdz's cell structure and method of assembly is adequate for certain
applications, the cell's production is very labor intensive, with many steps
and therefore costly. Since the extraction solvent is flammable, it is very
hazardous to handle, and if the electrolyte is flammable it can also cause
problems.
Yamashita et al. in U.S. Patent 6,207,720 Bl discloses another cell
structure and method of assembly, which employs a sole porous, thin
ceramic separator disposed between porous electrodes. Both electrodes and
the separator contain a binder which hold their particle materials together.
The cell is held together by a housing, or the separator is coated onto a
cathode or anode active layer, and is solidified by solvent evaporation, and
the cell is then fused together by pressing and heating to melt the binder or
by using a solvent capable of dissolving the binder to cause fusion. The solvent is removed and the cell is then activated by an electrolyte and
sealed.
Although Yamashita et al. in Patent No. 6,207,720 discloses an
improved cell assembly over the prior art patents, the resulting cell
structure has a major disadvantage, in that it produces a brittle ceramic
separator, or an entire cell that is brittle, which may cause low yield in
automated production process, or a size limitation due to cracking or
crumbling and separation of the cell. The cell also has solid metal foil
current collectors, which prevent fast evaporation of the solvent, and thus
prevent fast solidification in production, as well as preventing fast
activation by an electrolyte without using vacuum.
The U.S. Patent to Carlson et al. No. 6,306,545B1 discloses a
separator only, not a bonded cell or device and the separator is limited to a
pseudo-boehmite material layer.
The U.S. Patent to Kim et al. No. 6,268,087B1 discloses a laminated
polymer cell, which is laminated after the individual components are
activated by an electrolyte. It is not clear if the lamination means heat-
welding of the cell together, or if the cell is held together only by vacuum
packaging. The structure and methods are similar to Gozdz's cell above,
and therefore it is also done with many steps and is costly.
The lithium based electrochemical devices of the invention do not
suffer from the described problems and provide many positive advantages. SUMMARY OF THE INVENTION
It has now been found that lithium based electrochemical devices,
and for example lithium-ion cells, capacitors and the like can be made with
a single cell structure, which includes a porous first electrode with a binder,
5 which may be an anode coated on a porous expanded metal microgrid
current collector, a thin porous "ceramic separator with a binder, coated on
the first electrode active surface and solidified by solvent evaporation, a
thin layer of ionically conductive organic adhesive layer coated preferably
on the separator, a porous second electrode with a binder, which may be a
° cathode coated on a porous expanded metal microgrid current collector, and
a non-aqueous electrolyte The active surface of the second electrode faces
the adhesive layer on the separator and is pressed-on during assembly. The
ionically conductive polymeric adhesive layer may be solidified by solvent
evaporation, cooling, heating, electron beam radiation, or other well known
5 methods.
The principal object of the invention is to provide electrochemical
devices which preferably include a porous first electrode with a binder, a
porous ceramic separator with an ionically conductive adhesive layer, a
porous second electrode with a binder, and an electrolyte, housed in a
° moisture proof enclosure. A further object of the invention is to provide electrochemical
devices of the character aforesaid which can be single cell, bi-cell, single
layer or double layer capacitor, supercapacitor or other electrochemical
devices.
A further object of the invention is to provide electrochemical
devices of the character aforesaid which have improved electrochemical
stability and mechanical flexibility due to an organic adhesive layer.
A further object of the invention is to provide electrochemical
devices of the character aforesaid which have improved cycling
characteristics and short proof structure due to the immobilized ceramic
particles of the separator.
A further object of the invention is to provide electrochemical
devices of the character aforesaid which are particularly suitable for mass
production and which are non-flammable.
Other objects and advantageous features of the invention will be
apparent from the description and claims.
DESCRIPTION OF THE DRAWINGS
The nature and characteristic features of the invention will be more
readily understood from the following description taken in combination
with the accompanying drawings in which: FIG. 1 is a side elevational and sectional view of an electrochemical
device incorporating the invention, and
FIG. 2 is a top elevational plan view of the device of FIG. 1.
It should, of course, be understood that the description and drawings
herein are merely illustrative and that various modifications, combinations
and changes can be made in the structures disclosed without departing from
the spirit of the invention.
Like numerals refer to like parts throughout the several views.
DESCRIPTION OF THE PREFERRED EMBODIMENTS When referring to the preferred embodiments, certain teπriinology
will be utilized for the sake of clarity. Use of such terminology is intended
to encompass not only the described embodiment, but also technical
equivalents which operate and function in substantially the same way to
bring about the same result.
Referring now more particularly to the drawings and FIGS. 1 and 2
thereof, an electrochemical device 10 which in this instance is a lithium ion
cell, is therein illustrated.
The cell 10 includes a porous first electrode 11, which may be an
anode active material of well known type, which is coated onto a porous
expanded metallic microgrid current collector 12, which anode also
contains a binder. A thin porous ceramic separator 14 is provided which contains a binder (to be described), and electrically insulating particles
coated on the active surface 15 of the first electrode 11, which separator is
preferably solidified and immobilized by solvent evaporation. This
solidification also makes the separator bond to the first electrode 11. A thin
5 layer of ionically conductive organic adhesive 16 is then preferably coated
on the separator 14 opposite to the first electrode 11. A second porous
electrode 17 is provided with a binder, which may be a cathode active
material of well known type, coated onto a porous expanded metallic
microgrid current collector 19, which has the cathode active surface 20
° facing the adhesive layer 16 and separator 14. The cathode active surface
20 is pressed onto the ionically conductive adhesive layer 16 during
assembly of the cell (to be described). The second electrode 17 may be
smaller than the separator 14 to avoid shorting at the edges.
The adhesive layer 16 may be solidified by solvent evaporation,
5 cooling, heat, electron beam radiation or other well known methods as
desired and dependent on the adhesive used.
Since the electrodes 11 and 17, the separator 14 and the current
collectors 12 and 19 are porous, the solvent which may be contained in the
adhesive layer 16 is easily evaporated resulting in improved adhesion and
° permanent cell bonding.
After assembly as described above, a high boiling electrolyte (not
shown) is preferably added to the cell 10, which provides fast activation of the cell due to the porosity of the electrodes 11 and 17, and the separator
14. Because the solid adhesive layer 16 is in the middle of the cell, it does
not block the activation.
Any conventional well known electrolyte which is compatible with
5 the cell K) components may also be used, such as 1 mole Li PF6 in ethylene
carbonate and dimethyl carbonate having a 1 to 1 ratio.
The cell 10 after activation is placed into a moisture proof enclosure
25, with exiting, sealed terminals 26 and 27.
Both the electrode coatings may be well known slurries as used in
° the coating of electrodes of liquid electrolyte, lithium-ion rolled cells, but
the slurries in this invention are coated directly onto the expanded metal
microgrids 12, and 19 by a doctor blade, slot coating or reverse roll coating.
A support release film (not shown) is provided under the grids 12 and 19
until the coatings are solidified, and then calendered. The film (not shown)
5 is removed before calendering.
The binder of the electrodes 11 and 17 and separator 14 may be of
the same polymer, but preferably the polymers should be different for the
electrodes 11 and 17, and the separator 14.
For example, the separator 14 binder may be polyvinylidene (PVDF)
0 homopolymer, and the binder of the electrodes 11 and 17 may be polyvinyl
alcohol (PVOH), or vice versa. Since the different binders require different solvents, they will not
dissolve the opposing layer when coated-on wet.
The following examples are preferred for use with lithium-ion
polymer cells:
A. Example 1 of the ceramic coating slurry
1. 66g N-Methylpyrrolidinone (NMP), Aldrich
2. 4.5g PVDF Homopolymer, (Aldrich)
3. 90g alpha alumina Al2 03 ( 1 - 1.5U , low Na.)
The NMP component is useful in a range of 40 to 60 %
by percentage weight, the PVDF component is useful in a range of 2 to
10% by percentage weight, and the alpha alumina component is useful in a
range of 25 to 75% by percentage weight.
B. Example 2 of the ceramic coating slurry
1. 66g deionized H20
2. 4.5g PVOH, 90K M.W.
3. (3)90g LiF (1-1.5U).
It was also found that LiF improves ionic conductivity.
Other fluorides such as magnesium fluoride (MgF2) are also suitable
as are alumina and fluoride mixtures.
The H20 component is useful in a range of 40 to 60%, by percentage
weight, the PVOH component is useful in a range of 2 to 10% by
percentage weight, and the fluoride component is usefiil in a range of 25 to 75% by percentage weight. Other electrically insulating particles are also
useful, including organic particles, in similar slurries.
C. Example #1 of the ion-conductive adhesive
1. Solvent Dimethoxyethane (DME) (Aldrich) 88g
2. Polyvinylidene fluoride/hexafluoropropylene copolymer
PVDF/HFP 2801 (Atofina) 12g
3. Electrolyte 1.5M LiPF6 in EC/PC 30% 28g
(or 2M LiBF4 in EC/PC 30%)
4. Heat to 50°C and mix in a closed vessel, then cool to room
temp.
where M = mole
The DME component is useful in a range of 40 to 95% by
percentage weight, the PVDF/HFP component is useful in a range of 5 to
20% by percentage weight, and the electrolyte is useful in a range of 10 to
45% by percentage weight.
D. Example #2 of the ion-conductive adhesive
1. PVDF homopolymer (Aldrich) 30g
2. Electrolyte 2M LiBF4 in EC/PC 30% 70g
3. Heat to 180°C and mix under inert atmosphere (=hot melt)
4. Coat hot and let cool to room temp, after cell assembly. The PVDF component is useful in a range of 5 to 50% by percentage weight,
and the electrolyte component is useful in a range of 50 to 95% by percentage
weight.
Other well known lithium salts, such as Lithium Methide, Lithium
5 Hexafluoroarsenate, Lithium Imide Lithium Triflate, Lithium Perchlorate and
Lithium Beti are also suitable.
E. Examples of highly conductive high boiling (low flammability
electrolytes
1. 1 M LiPF6 in EC/PC 70/30% (7:3) ratio
° 2. 1M LiBF4 in EC/PC 70/30% (7:3) ratio
3. 2M LiBF4 in EC/GBL 80/20% (4:1) ratio
4. 2M LiBF4 in EC (Eutectic),
or their mixtures.
Other well known lithium salts are also suitable for the above electrolytes.
5 The lithium salt components are useful in a range of 0.5M to 3M,
the ethylene carbonate (EC) component is useful in a range of 40 to 90% by
percentage weight, the propylene carbonate (PC) component is useful in a
range of 10 to 70% by percentage weight, and the Gammabutyrolactone
(GBL) component is useful in a range of 5 to 70% by percentage weight.
0 It has also been found that the viscous organic ion-conducting
adhesives and high boiling (low-flammability) electrolyte liquids require more lithium salt than conventional flammable electrolyte liquids in order
to overcome their higher viscosity (resistance).
The main advantage of the cell of the invention over the prior art is
in providing a safer high energy density and power density device with a
thin, flexible structure, due to the organic adhesive layer, and a short proof
structure, due to the adjacent immobilized porous ceramic particle layer and
the high boiling, low flammability electrolyte. Manufacture of the cell of
the invention is also easier due to lack of plasticizer, extraction step, and
welding. The separator layer may be 1 mil or thinner, and the adhesive
layer may be 1 mil or thinner.
It should be noted that the mixing and coating of the adhesive, and
the cell assembly should be done under inert atmospheric conditions, and
that the electrodes and the separator should be dried under vacuum for eight
hours before gluing.
While the electrochemical device described herein is a lithium-ion
single cell, the construction is equally applicable to bi-cell structures, as
well as single or double layer capacitors, supercapacitors, and other
electrochemical devices.
It will thus be seen that safe electrochemical devices of high energy
density and power density have been provided with which the objects of the
invention have been achieved.

Claims

We Claim:
1. A lithium based electrochemical device comprising
at least two porous electrodes,
said electrodes include expanded metal microgrids
having active materials coated thereon,
at least one porous ceramic separator between said electrodes,
said separator having one side in bonding contact with said
first electrode active material,
an organic ion-conductive adhesive layer on the other side of
said separator in adherent contact with said separator and said other
electrode,
a non-aqueous electrolyte in contact with said electrodes,
and said separator, and
an enclosure surrounding and containing said device.
2. An electrochemical device as defined in claim 1, in which
said electrodes are an anode and a cathode.
3. An electrochemical device as defined in claim 1, in which
said separator contains particles of an electrically insulating
material and a binder.
4. An electrochemical device as defined in claim 3, in which
said particles are alpha alumina particles.
5. An electrochemical device as defined in claim 3, in which said particles are inorganic lithium fluoride particles.
6. An electrochemical device as defined in claim 3, in which
said particles are inorganic fluoride particles.
7. An electrochemical device as defined in claim 3, in which
said particles are a mixture of inorganic fluoride and alumina
particles.
8. An electrochemical device as defined in claim 1, in which
said adhesive is PVDF/HFP copolymer based and contains at
least one aprotic liquid and at least one salt. 0
9. An electrochemical device as defined in claim 1, in which
said adhesive is PVDF homopolymer based and contains at
least one aprotic liquid and at least one salt.
10. An electrochemical device as defined in claim 1, in which
said electrolyte is high boiling and essentially non-flammable.
11. An electrochemical device as defined in claim 1 , in which
said electrolytes contain a binder.
12. An electrochemical device as defined in claim 3 and 11, in
which
said separator binder is of a different polymer than said
° electrodes' binders, and uses a different solvent.
13. An electrochemical device as defined in claim 1, in which
said device is a bi-cell.
14. An electrochemical device as defined in claim 1, in which
said device is a capacitor.
15. An electrochemical device as defined in claim 1, in which
said device is a supercapacitor.
16. An electrochemical device as defined in claim 1, in which
said device is a double layer capacitor.
17. An electrochemical device as defined in claim 1, in which
said at least one electrode is smaller than said separator.
18. An electrochemical device as defined in claim 1, in which
said separator comprises a mixture of N-methylpyrrolidinone
in the range of 40 to 60% by percentage weight,
polyvinylidene fluoride in the range of 2 to 10% by
percentage weight, and alpha alumina in the range of 25% to
75% by percentage weight.
19. An electrochemical device as defined in claim 1, in which
said separator comprises a mixture of H20 in the range of
40% to 60% by percentage weight, polyvinyl alcohol in the
range of 40% to 90% by percentage weight, and lithium
fluoride in the range of 25% to 75% by percentage weight.
20. An electrochemical device as defined in claim 1, in which
said separator is coated with an adhesive which is a mixture
of dimethoxy ethane in the range of 40% to 95% by percentage weight, polyvinylidene
fluoride/hexafluoropropylene in the range of 5% to 20% by
percentage weight, and a lithium based electrolyte in the
range of 10% to 45% by percentage weight.
21. An electrochemical device as defined in claim 1, in which
said separator is coated with an adhesive which is a mixture
of polyvinylidene fluoride in the range of 5% to 50% by
percentage weight, and/or a lithium based electrolyte in the
range of 50% to 95% by percentage weight.
EP02807507A 2002-06-08 2002-06-08 Lithium based electrochemical devices having a ceramic separator glued therein by an ion conductive adhesive Withdrawn EP1512187A1 (en)

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Application Number Priority Date Filing Date Title
PCT/US2002/018175 WO2003105258A1 (en) 2002-06-08 2002-06-08 Lithium based electrochemical devices having a ceramic separator glued therein by an ion conductive adhesive

Publications (1)

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EP1512187A1 true EP1512187A1 (en) 2005-03-09

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WO (1) WO2003105258A1 (en)

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US9843027B1 (en) 2010-09-14 2017-12-12 Enovix Corporation Battery cell having package anode plate in contact with a plurality of dies
WO2013112135A1 (en) * 2012-01-24 2013-08-01 Enovix Corporation Ionically permeable structures for energy storage devices
KR102230556B1 (en) 2012-08-16 2021-03-22 에노빅스 코오퍼레이션 Electrode structures for three-dimensional batteries
EP4358271A3 (en) 2013-03-15 2024-07-24 Enovix Corporation Three-dimensional batteries
EP3800730B1 (en) 2015-05-14 2022-08-24 Enovix Corporation Secondary batteries with longitudinal constraints
EP3320573A1 (en) * 2015-07-09 2018-05-16 DSM IP Assets B.V. Solid polymer electrolyte
SG10202106068XA (en) 2016-05-13 2021-07-29 Enovix Corp Dimensional constraints for three-dimensional batteries
KR102525366B1 (en) 2016-11-16 2023-04-26 에노빅스 코오퍼레이션 Three-dimensional batteries with compressible cathodes
CN111684638A (en) 2017-11-15 2020-09-18 艾诺维克斯公司 Electrode assembly and secondary battery
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US11211639B2 (en) 2018-08-06 2021-12-28 Enovix Corporation Electrode assembly manufacture and device
JP2023547993A (en) 2020-09-18 2023-11-15 エノビクス・コーポレイション Apparatus, system, and method for manufacturing electrodes for use in batteries
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WO2003105258A1 (en) 2003-12-18

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