HK1196029A - Rechargeable alkaline metal and alkaline earth electrodes having controlled dendritic growth and methods for making and using the same - Google Patents

Description

Rechargeable alkali and alkaline earth electrodes with controlled dendrite growth and methods of making and using the same

Cross Reference to Related Applications

The present patent application claims priority from yet-to-be-approved U.S. provisional patent sequence No. 61/486946 filed on 5/17/2011, from yet-to-be-approved U.S. provisional patent sequence No. 61/498192 filed on 6/17/2011, and from yet-to-be-approved U.S. provisional patent sequence No. 61/565101 filed on 11/30/2011, the entire contents of which are incorporated herein by reference.

Background

It has long been desirable to use lithium metal as the anode to build a rechargeable lithium battery or battery system with the highest anode specific capacity. However, the growth of lithium metal dendrites creates a serious technical barrier for the development of such batteries. Recently, modifications of lithium metal batteries, such as lithium ion batteries, have introduced some success. However, current modifications have limitations and inefficiencies that do not occur with batteries using lithium metal as the anode.

Generally, lithium metal batteries include an anode and a cathode separated by an electrically insulating separator or "separator" and operatively connected by an electrolyte solution. During charging, positively charged lithium ions move from the cathode through the permeable separator to the anode and are reduced to lithium metal. During discharge, lithium metal is oxidized to positively charged lithium ions, which move from the anode, through the separator and onto the cathode, while electrons move through an external load, from the anode to the cathode, generating an electric current and providing power to the load. During repeated charging and discharging, lithium dendrites begin to grow from the surface of the anode. Dendritic lithium deposits, sometimes referred to as bryozoan lithium, eventually break apart through the separator and reach the cathode, causing an internal short circuit and rendering the battery inoperable. The formation of lithium dendrites is inherently unavoidable during the charging and discharging of the lithium metal battery. Thus, there remains a need for a lithium electrode battery system that does not suffer from dendrite growth while maintaining the cycling capability, ionic conductivity, voltage and specific capacity of the battery. The present novel technique addresses these needs.

Drawings

FIG. 1 is a schematic diagram of a lithium-ion battery in accordance with a first embodiment of the present novel technique.

Fig. 2A is a perspective view of the separator of fig. 1.

Fig. 2B is an exploded view of the surface of the separator of fig. 2.

Fig. 3A is a first perspective view of the composite electrode of fig. 1.

Fig. 3B is a second perspective view of the composite electrode of fig. 1.

Fig. 3C is a third perspective view of the composite electrode of fig. 1.

Fig. 3D is a fourth perspective view of the composite electrode of fig. 1.

Figure 4 is a perspective view of a second embodiment button cell embodiment of the present novel technology.

Fig. 5 is an enlarged elevational view of a dendrite grown from the surface of the electrode of fig. 1.

FIG. 6 is an exploded view of the surface of the baffle of FIG. 1 partially coated with FNC.

FIG. 7 is a flow chart of a third embodiment of the present novel technique illustrating a method of forming a dendrite seeding material.

FIG. 8 is a flow chart illustrating a method of controlling metal dendrite growth according to a fourth embodiment of the present novel technique.

FIG. 9 is a flow chart of a fifth embodiment of the present novel technique illustrating a method of extending battery life.

FIG. 10 is a flow chart of a sixth embodiment of the present novel technique illustrating a method of making a septum coated with FNC.

Detailed Description

For the purposes of promoting and understanding the principles of the novel technology and setting forth the best mode of operation presently understood, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the novel technology is thereby intended, such alterations and further modifications in the illustrated novel technology, and such further applications of the principles of the novel technology as illustrated therein being contemplated as would normally occur to one skilled in the art to which the novel technology relates.

As shown in fig. 1-10, the present novel technology relates to a rechargeable lithium metal electrochemical storage cell 10 having a lithium metal electrode 20. Referring to fig. 1, a rechargeable lithium electrode cell 10 is shown having a lithium metal cathode section 12 and a lithium metal anode section 14. Separator 50 is positioned between anode 14 and cathode 12. The separator 50 is typically coated with a layer 80 of functionalized nanocarbon particles 40. The separator 50 includes an anode facing side 53 and a cathode facing side 52, and is typically coated with a thin or very thin film 80 of Functionalized Nanocarbon (FNC) particles 40, more typically about 0.1 μm thick, and is typically oriented to face the surface 70 of the lithium metal electrode 20. The gap 26 is filled with electrolyte 25 between the lithium metal electrode 20 and the FNC-coated separator 60. The functionalized nanocarbon particles 40 typically have Li + ions immobilized on the surface 65 of the layer 80 of nanocarbon particles 40. The FNC film 80 is electrically connected to the lithium metal electrode 20. When the lithium metal electrode 20 is charged, the lithium dendrites 11 extend from the surface 70 of the lithium metal electrode 20 toward the FNC coated separator 60. Meanwhile, the dendrites 55 extend from the surface 65 of the FNC film 80 toward the surface 70 of the lithium metal electrode 20. The dendrite 55 grows in the passing plane direction 94 of the lithium metal electrode 20 and the FNC-coated separator 60.

Referring to fig. 5, the growth of dendrites 11, 55 is driven by the potential difference (Δ E) between the leading end (Et) 59 and the base (Eb) of the respective dendrite 11, 55. As a result of the circulation, the dendrites 11, 55 continue to extend towards each other; eventually, the dendrites 11, 55 contact each other and the potential difference (Δ E) the dendrites 11, 55 are about zero because the FNC film 80 and the lithium metal electrode 20 have the same potential. Thus, dendrite 11, 55 growth is retarded or stopped along the through plane direction 94. In subsequent cycles, the dendrites 11, 55 may grow in a direction perpendicular to the long axis of the respective dendrite 11, 55 and parallel to the plane of the lithium metal electrode 20 (also referred to as the in-plane direction 84), which prevents the dendrite 11, 55 from piercing the permeable or selectively permeable membrane 50, as shown in fig. 3A-3D. Finally, from the intersection of the lithium dendrites 11, 55, a lithium regeneration surface 70 may be formed. Thus, a composite lithium metal electrode 20 is formed, wherein the lithium electrode 20 is provided with a thin carbon layer 80.

Although lithium is generally specifically described herein as an electrode metal, the storage battery 10 may alternatively include other alkaline earth and/or alkaline earth metal elements and combinations thereof as electrode materials.

Two types of exemplary configurations for batteries utilizing a lithium metal dendrite/electrode system include a symmetric battery 400, where a lithium metal electrode 420 is used as an anode 414 and a cathode 412, with a lithium/polymer/lithium (anode/electrolyte/cathode = a/E/C) configuration, enabling lithium dendrite mechanism studies or lithium polymer battery systems; and an asymmetric cell 500 in which lithium metal is the anode 514, with different materials selected for the cathode 512, such as lithium/polymer electrolyte/V2O 5, lithium/liquid electrolyte/graphite, lithium/polymer electrolyte/graphite, and lithium/polymer electrolyte/FePO 4. The symmetric cell 400 provides a better medium for lithium metal dendrite growth and can accelerate cycling tests, while the asymmetric cell 500 is closer to field applications.

As shown in fig. 5, dendritic growth is essentially unavoidable because the metallurgical properties of the lithium metal surface lead to surface defects of the lithium metal electrode after application of either mechanical stress or plating/deplating cycles. While the configurations known in the art are focused solely on stopping dendrite 11 growth, the novel cell design 10 focuses on controlling the direction of growth of the lithium metal dendrites 11, 55.

As shown in fig. 9, an embodiment 800 of the novel electrode 20 may have a carbon coating of functionalized nanocarbon particles (FNCs) 80 on the separator 50 that is positioned 801 in the electrolyte 25 and causes lithium dendrites 11, 55 to grow 803 simultaneously from the surface 51 of the lithium metal electrode 20 and the surface 65 of the FNC coated separator 60. Electrolyte 25 is placed in the gap 26 between the 802 electrode 20 and the FNC coated separator 60. The dendrites 11, 55 grow 803 after repeated charging and discharging 804 of the battery 10. Dendrites 11, 55 contact each other 805 and when contact occurs, dendrites 11, 55 stop extending in through plane direction 94 due to the zero potential difference resulting from the contact. Control of the dendrite growth direction 800 occurs through contact 805 between the separator dendrite 55 and the electrode dendrite 11, which is coated with FNC. After multiple bonding of the dendrites 11, 55, a lithium-regenerated lithium surface 70 is formed 806.

Establishing a zero potential difference provides the rechargeable lithium metal electrode 20 with high specific capacity, high cycling performance, and high safety. Thus, the rechargeable lithium metal electrode system 10 can be implemented in a variety of lithium batteries, including lithium polymer, lithium-air, and lithium metal oxide battery systems, as well as any other battery system in which a lithium metal anode 14 is used and which yields benefits for electronics, electric and hybrid electric vehicles, large scale energy storage, and the like.

In general, the challenge of developing high specific capacity and rechargeable lithium metal electrodes 20 for different lithium batteries (i.e., lithium polymer, lithium air, lithium ion, etc.) has been to stop the electrode dendrite 11 growth during cycling 803. The lithium metal electrode 20 has an inherent metallurgical tendency to form dendrites 11, with dendrite 11 growth driven by the potential difference between the base 57 and the dendrite front end 59. Therefore, the growth of the lithium electrode dendrite 11 is inevitable. However, the present system 800 incorporates, rather than avoids, a dendrite growth mechanism.

In one embodiment, the rechargeable lithium metal electrode 220 is used in other lithium battery systems such as lithium polymer and lithium air, and may be manufactured by coating the FNC layer 280 on the polymer electrolyte membrane 200, which is used as the electrolyte 225 in lithium polymer batteries and lithium air batteries. These FNC coated polymer electrolytes 225 are typically incorporated as an intermediate layer 280 and assembled into a soft packed lithium air cell 285. Such polymer electrolyte membranes 260 may include these poly (ethylene oxide) (PEO), poly (vinylidene fluoride) (PVdF), poly (acrylonitrile) (PAN), and other polymer electrolytes, which are widely used for lithium polymer batteries and lithium air batteries.

Further, the FNC coated spacer 60 may be manufactured in a variety of modes. The FNC layer 80 functions in the novel lithium metal electrode 20 because the fixed Li + ions 30 in the FNC layer 80 act as "seeds" 31 for the formation of lithium metal dendrites 55 on the FNC layer 80. The FNC layer 80 is generally porous, allowing the FNC aggregates to be bonded 605 together by a network of binder 604 to form a rigid structure 606 to maintain 607 the integrity of the layer 80. Layer 80 is typically very thin, having four main properties: 1) good pore structure to facilitate Li + ions to pass through, 2) high conductivity to reduce internal impedance, 3) high coverage of Li + ions 30 on the nanocarbon surface 65 to facilitate formation of lithium metal dendrites 55, and 4) good adhesion to the polymer separator 50 or polymer electrolyte membrane. All these properties are similar to those used for the catalyst layer in a fuel cell,(i.e., porous layer for diffusion of gas and water, electrical conductivity necessary for gas reaction, SO for proton conduction₃Good adhesion of catalyst layers on polymer electrolyte membranes for covering, and for durability). The thinner the FNC layer 80, the less the loss of specific capacity of the lithium metal electrode 20.

The morphology of the FNC layer 80 depends on how the layer is made 601. Such techniques for applying 609 layers 80 include (1) spray coating, (2) knife coating, (3) brush hand painting, and the like. The carbon may be selected from sources including carbon black, nanographite, graphene, and the like. It has been found that the higher the degree of graphitization, the higher the chemical stability. The nano-carbon particles 40 may be made of carbon black, which is inexpensive, but has an amorphous structure rather than a graphite structure. Graphene can also be used and has unique properties such as high electronic conductivity, high modulus, and high surface area.

The morphology of the FNC layer 80 is also affected by the ink formulation. To produce a thin carbon layer, the first step is to mix 600 a carbon source with a solvent to produce a uniformly dispersed suspension 603. To form such well-dispersed carbon inks, the solvent type is carefully selected based on polarity (i.e., dielectric constant) and their hydrophobicity to match these carbon aggregates and binders. This mixture 602 is also referred to as an "ink formulation". The type of carbon and solvent in the ink will affect the morphology of the thin FNC layer 80. The type of adhesive 33 also affects the adhesion of the carbon layer 80 on the separator 50. Generally, the adhesive 33 has a similar chemical structure to the separator/electrolyte membrane 50 so that they can be fused 605 together by hot pressing or other techniques to form a well-bonded interface 62 between the carbon layer 80 and the separator/electrolyte membrane 50.

The immobilized Li + ions 30 on the surface of the nanocarbon particles 40 serve as "seeds" 31 for the formation of lithium dendrites 55 on the FNC-coated separator 60. The immobilization of the Li + ions 30 is accomplished by forming 900 a dendritic seeding material 61, such as by diazo reaction or similar means 902 on a suitable 901 carbon separator 50, to immobilize the SO₃The H groups 902 are chemically attached to the carbon surface 65, allowing the carbon separator to50 becomes functionalized 903. Then, the SO attached₃H exchanges with Li + ions 30 to immobilize the Li + ions 30 on the surface 65. Thus, a dendrite seeding material 61 is formed 907. The dendrite seeding material 61 is typically carbonaceous, but may also be a metal matrix such as Li, Na, K, Al, Ni, Ti, Cu, Ag, Au, and combinations thereof. The seed material 61 may also be a functionalized metal matrix, such as a self-assembled monolayer structure composed of Au, with thiol-terminated organic molecules containing at least one functional group, such as SO3-M +, COO-M +, and NR3+ X-; conductive organic polymers such as polyacetylene, polyphenylacetylene, polypyrrole, polythiophene, polyaniline, and polyphenylene sulfide, or functionalized conductive organic polymers, wherein the functional group is chemically bonded to the polymer. These materials 61 may be deposited using conventional physical deposition techniques such as mechanical delamination or physical vapor deposition techniques such as sputtering and the like.

The novel technique allows for the attachment 903 of different functional groups to the carbon surface 65, such as by diazo reaction or the like. In this reaction, the functional group Y is diazotized XN by introduction 904₂C₆H₄Y (where Y = sulfonate, S03-M +, carboxylate, COO-M +; and tertiary amines, NR3+ X; etc.) is attached 903 to carbon surface 65. The attachment of the different chemical groups not only provides a platform for fixing the Li + ions 30 to the FNC surface 65, but also changes the surface energy of the carbon particles, which can be used as a tool for adjusting the surface hydrophobicity of the carbon film 80, and aids in the ink formulation 603.

The bonding 609 of the FNC layer to the separator/polymer electrolyte 50 affects the cycle life of the novel lithium metal electrode 20. A good interface 62 between the 608FNC layer 80 and the separator/electrolyte membrane 50 is typically formed. This is primarily dependent on the network of binder 33 in the FNC layer 80 and the technique used to form the interface 62. Such a catalyst layer may be subjected to long term durability testing for thousands of hours, due in part to the adhesive 33 in the retention 607FNC layer 80 being bonded to the separator/electrolyte membrane 50. Such TEM observation of the catalyst/membrane interface 62 will show little or no delamination after about 2000 hours of durability testing. Hot pressing is one of the techniques used for manufacturing, and the parameters of hot pressing (i.e., temperature, pressure, and time) allow for systematic control of the process.

The morphology (i.e., surface area, pore structure, and geometry) of the FNC layer 80 on the membrane 50 has a significant impact on the performance of the novel metal electrode 20. The FNC layer 80 porosity 81 (i.e., pore size distribution, and pore volume) is a factor in controlling the direction of dendrite growth 700 because it affects the presence 705 of metal cations 30 on the FNC membrane surface 65 and the addition 703 of dendrite seed material 61. The pore structure generally allows the metal ions 30 to pass smoothly during the cycling 704, but does not form dendrites inside the pores that would prevent the metal ions 30 from diffusing. Thus, the determination 701 and fabrication 702 of a suitable FNC layer 80 having a porosity 81 is useful in allowing the dendrites 11, 55 to exist 706 and ultimately form 707 the second metal layer 70. On the other hand, the FNC layer 80 must adhere to the separator/electrolyte membrane 50, and the diffusion barrier from the formed interface 62 (if present) should be minimized.

Generally, by varying the thickness 89 of the FNC film 80 relative to the thickness 29 of the lithium metal electrode 20, the specific capacity of the rechargeable metal electrode 20 may be affected. The examples herein relate to novel technology and different embodiments, and are not intended to limit the scope of the novel technology to the modes and embodiments discussed herein.

Example 1:

the effect of different carbon coating layers on the specific capacity of the lithium metal composite electrode 20 was approximately calculated and is shown in table 1. For example, for a carbon coating layer 80 of 0.1 μm thickness, the corresponding specific capacity loss of the lithium metal electrode 20 is only 0.026%. Even for FNC films 80 of 4 μm thickness, the corresponding loss in specific capacity was only 0.53%. Therefore, the carbon coating layer 80 has a negligible effect on the specific capacity of the lithium metal electrode 20. The thin carbon coating 80 retains the advantage of the high specific capacity of the lithium metal electrode.

TABLE 1

Influence of carbon film thickness on specific capacity of lithium metal electrode

Thus, carbon has proven to be very stable over a wide potential window. The composite lithium electrode with a very thin carbon film is very stable. Carbon black is useful in many battery systems (i.e., Zn/MnO)₂In particular lithium ion batteries (as anode) and Li-SOCl₂In a battery (as a carbon cathode).

Referring to fig. 4, the lithium metal anode 14 is assembled with a separator 350 (thickness =25 μ M) coated with a thin nanocarbon layer 80 of functionalized carbon nanoparticles 340 (δ =3.2 μ M) and 1.2M LiPF in ethylene carbonate/ethyl methyl carbonate (EC: EMC =3: 7) by using₆Into the configuration of the button cell 300 by LiPFeO₄A cathode 312. Button cells of the same assembly but without the nanocarbon coating 380 were used as a benchmark for comparison. One concern with the use of such a carbon coating 380 is whether the addition of the FNC layer 380 to the separator 350 will result in an increase in internal resistance from the carbon layer 380, blocking the pores of the separator 350, thereby preventing Li + ions 330 from diffusing through, and thus reducing the power performance of the battery 300. It is apparent, however, that the application of the carbon layer 380 to the separator 350 does not result in an increase in the internal resistance of the battery 300, but rather results in a slight decrease in resistance. The Li/FNC battery 300 has a slightly higher discharge voltage than the reference lithium battery. The same trend was observed even after 500 cycles. For the reference cell, noise was observed, which was attributed to the formation of dendrites 355. Furthermore, the same phenomenon of reducing internal impedance has been observed during charging.

With respect to capacity, the battery 300 is not balanced, and the capacity of the battery 300 is represented by LipFeO₄A cathode 312 restriction; if a suitably high energy density cathode is used (e.g. V)₂O₅Aerogel or air cathode), then of cell 300Much higher capacities are expected. The lithium metal electrode 314 using the FNC layer 380 exhibited excellent cyclability, and the capacity was about 84% after 500 cycles. The estimated capacity fade rate of the novel lithium metal electrode cell 300 after the first 45 cycles was only 0.026%/cycle. Based on this decay rate, the cycle life of such batteries can typically reach at least 500, more typically at least 725, and still more typically at least 1000 cycles, with 80% capacity (a dead definition of a battery in an Electric Vehicle (EV) application). This decay rate (0.026%/cycle) for the novel lithium metal electrode 320 in button cell 300 is likely to be due to LiFePO₄Degradation of the cathode 312 results because the button cell 300 is sealed at ambient atmospheric pressure, which may allow moisture to be introduced into the cell 300. Moisture and LiPF₆Reaction takes place to form HF, which can react with LiFePO₄Reactions occur, resulting in degradation. Thus, if the button cell 300 is sealed in, for example, an argon filled glove box, the true decay rate of the novel lithium metal electrode 320 should be much lower than 0.026%/cycle.

Example 2:

referring to FIG. 6, FNC coated baffle 60 was investigated by SEM analysis after repeated cycling. Lithium metal dendrites 55 are observed on the surface 65 of the FNC coated separator 60, facing the surface of the lithium metal electrode 20. Furthermore, the lithium dendrites 55 form a single layer rather than being aggregated into loosely arranged dendrites. The FNC layer 80 has a thickness 89 that measures about 3 μm, while the lithium dendrite 70 layer is about 20 μm thick. Referring to FIG. 6, and to further illustrate the function of the FNC layer 80 for inducing the formation of lithium metal dendrites 55, the separator 50 is coated with the FNC layer 80 on half of the surface area, while the other half is uncoated. No dendrites 55 are formed on the uncoated regions of the separator 50. No lithium dendrites 55 were found on the opposite side of the FNC coated separator 50. Some large-sized particles (more than 50 μm) can be seen observed under the separator 50; these large particles may originate from the SEM conductive paste used to adhere the sample of separator 50 to the SEM aluminum pan.

In another embodiment, the layer 80 formed on the electrochemical separator 50 to enable dendrite growth toward the metal anode 14 is a thin metal layer 80. Dendrites 55 growing from separator 50 contact dendrites 11 growing from metal anode 14, shorting the circuit, thereby preventing dendrites 11 growing from anode 14 from heading toward separator 50 to reach and pierce separator 50. The anode 14 is usually lithium, but may be sodium or the like. The metal layer 80 on the separator 50 is typically lithium, but may also be sodium or another conductive metal, a conductive polymer, an organometallic matrix, a functionalized conductive polymer, or the like. More typically, layer 80 is a non-reactive metal, such as nickel. The metal layer 80 on the separator 50 is typically formed thin enough so that its resistivity is high, typically high enough so that the layer 80 is not susceptible to electrical or other degradation. Optionally, thin metal layer 80 may be functionalized after deposition onto separator 50.

While the novel techniques have been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character. It is to be understood that these embodiments have been shown and described in the foregoing description as the best mode and enabling requirements. It should be understood that a nearly limitless number of insubstantial changes and modifications to the embodiments described above may be readily made by those skilled in the art, and it would be impractical to attempt to describe all such embodiment variations in this specification. It is therefore to be understood that all changes and modifications that come within the spirit of the novel technology are desired to be protected.

Claims (33)

1. An electrode separator comprising:

an electrically insulating separator member having an anode-facing side and a cathode-facing side; and

a layer of functionalized nanocarbon particles adhered to the anode facing side of the electrically insulating barrier member; and is

Wherein the functionalized nanocarbon particles are functionalized due to ion-associated metal cations used for seed dendrite growth.

2. The separator of claim 1, wherein the functionalized nanocarbon particles are selected from the group consisting of carbon black, graphene, graphite, nanographite, amorphous carbon, and combinations thereof.

3. The separator of claim 1, wherein the metal cation is ionically associated with a functional group selected from the group consisting of sulfonate, carboxylate, tertiary amine, diazonium salt, and combinations thereof.

4. The separator of claim 1, wherein the electrically insulating separator member is permeable to an organic electrolyte containing a metal salt.

5. The separator of claim 4, wherein the metal is selected from the group consisting of lithium, sodium, potassium, calcium, magnesium, and combinations thereof.

6. A lithium metal battery cell comprising:

an electrolyte medium;

a cathode in the electrolyte medium;

a lithium-containing anode in the electrolyte medium and spaced apart from the cathode;

a separator having an anode facing side and a cathode facing side disposed between the lithium-containing anode and cathode; and

a plurality of lithium-functionalized nanocarbon particles operatively connected to the anode-facing side of the separator;

wherein the separator is electrically insulating and electrolytically permeable.

7. The battery cell of claim 6 wherein a plurality of dendrites extend from the lithium-containing anode toward the separator and a plurality of dendrites extend from an anode-facing side of the separator toward the lithium-containing anode.

8. The battery cell of claim 7 wherein the plurality of dendrites combine in the electrolyte medium and have a potential difference of about zero.

9. The battery cell of claim 8 wherein the plurality of dendrites define a regenerated lithium metal layer.

10. The battery cell of claim 6 wherein the battery cell is a button cell.

11. The battery cell of claim 6 wherein the battery cell is rechargeable.

12. The battery cell of claim 6 wherein the battery cell is symmetrical.

13. An apparatus for extending battery life, comprising:

an electrode having a metal portion, wherein the metal portion is selected from the group consisting of lithium, calcium, magnesium, sodium, potassium, and combinations thereof;

an electrolyte permeable membrane; and

a metal dendrite seeding material disposed between the electrode and the membrane;

wherein the electrode, membrane and metal dendrite seeding material are located in an electrolyte matrix;

wherein at least one dendrite extends from the electrode toward the electrolyte permeable membrane, incorporating at least one dendrite extending from the dendrite seeding material.

14. The device of claim 13 wherein the metal dendrite seeding material is a plurality of metal functionalized carbon nanoparticles and wherein the metal is selected from the group consisting of lithium, calcium, magnesium, sodium, potassium, and combinations thereof.

15. The device of claim 13, wherein dendrites extending from the electrode and dendrites extending from the dendrite seeding material combine to form a regenerated metal portion.

16. A method of extending battery life, comprising:

a) positioning a dendrite seeding material in an electrolyte solution disposed between a metal-containing electrode and an electrolyte permeable separator membrane;

b) growing a metal dendrite from a lithium dendrite seeding material towards a lithium containing electrode; and

c) contacting a metal dendrite extending from the metal containing electrode with a metal dendrite extending from a metal dendrite seeding material;

wherein the electrolyte comprises metal ions.

17. The method of claim 16 wherein contact between lithium dendrites extending from the lithium containing electrode and lithium dendrites extending from the lithium dendrite seeding material substantially stops the growth of the contacting lithium dendrites along the long axis.

18. The method of claim 16, further comprising:

d) entangling lithium dendrites extending from the lithium containing electrode with lithium dendrites extending from the lithium dendrite seeding material; and

e) a lithium layer from the entangled lithium dendrites is formed.

19. A method of making a dendrite seeding separator material comprising:

a) identifying the surface of the carbon separator;

b) functionalizing the surface of the carbon separator with a chemically bound anion-containing structure;

c) introducing a neutral metal salt to the functionalized carbon separator surface;

d) reacting the neutral salt to produce a metal cation and an anion; and

e) the metal cation is attracted to the chemically bound anion.

20. The method of claim 19, wherein the metal is selected from the group consisting of lithium, calcium, magnesium, sodium, potassium, and combinations thereof.

21. The method of claim 20, wherein the metal cation is weakly bound to the chemically bound anion.

22. A method for controlling metal dendrite growth in a battery cell comprising:

a) determining a desired porosity value for the electrolyte membrane;

b) providing a porosity value to the electrolyte membrane;

c) implanting a dendrite seeding material onto the electrolyte membrane;

d) introducing a gradient of metal cations from a metal electrode through the electrolyte membrane;

e) immobilizing a portion of the metal cations on an electrode facing surface of the electrolyte membrane; and

f) directional dendrite growth is promoted on the membrane facing side of the electrode and on the electrode facing side of the membrane.

23. The method of claim 22 further comprising preventing dendrite growth in an in-plane direction of the electrolyte membrane until the electrode dendrites bind membrane dendrites.

24. The method of claim 22 wherein the electrolyte membrane is selectively permeable.

25. The method of claim 24 wherein the electrolyte membrane comprises a layer of functionalized nanocarbon particles.

26. A method of making an electrolyte polymer membrane, comprising:

mixing a particulate carbon source with a plurality of solvents to form a suspension;

determining a binding element to affect adherence of the suspended carbon particles to the permeable membrane;

applying the binding element to a permeable membrane to define an adhesive membrane;

applying the suspension to the adhesive film; and

forming an interface between the suspensions.

27. The method of claim 26, wherein the suspension is a plurality of functionalized nanocarbon particles.

28. The method of claim 26, wherein the carbon substance is selected from the group consisting of carbon black, graphene, graphite, nanographite, and combinations thereof.

29. The method of claim 26, wherein the binding element and electrolyte polymer film have substantially similar chemical compositions.

30. The method of claim 26, wherein the application of the suspension is achieved by a process selected from the group consisting of hot pressing, spraying, knife coating, brushing, and combinations thereof.

31. The method of claim 26, wherein the suspension is uniformly dispersed.

32. The method of claim 26, further comprising maintaining the adhesiveness of the suspension by the binding element.

33. A method for controlling metal dendrite growth in an electrochemical cell comprising:

a) coating an electrolytically permeable and electrically insulating film with a non-reactive metal coating;

b) functionalizing the non-reactive metal coating to produce a functionalized non-reactive metal coating;

c) positioning an electrolyte solution between the electrode and the functionalized non-reactive metal coating;

d) introducing a gradient of metal cations from a metal electrode through the electrolytically permeable and electrically insulating film;

e) immobilizing a portion of the metal cation on the functionalized non-reactive metal coating; and

f) promoting the growth of directed dendrites from the electrode and from the membrane through the electrolyte solution.