JP2014506381A - Surface-mediated lithium ion exchange energy storage device - Google Patents

Abstract

(A) an anode (cathode) comprising a cathode active material having a surface area that is functional or non-functionalized to take up or store lithium therein; and (b) functionalized or non-functionalized therein. A cathode comprising an anode active material having a surface area that takes up or stores lithium in the anode (anode), (c) a porous separator disposed between the two electrodes, and (d) lithium in physical contact with the two electrodes A surface-mediated lithium ion exchange energy storage device comprising a containing electrolyte. In one embodiment, at least one of the two electrodes includes a lithium source prior to the first charge or first discharge cycle of the energy storage device.
[Selection] Figure 2

Description

  The present invention is based on the research results of a project supported by the National Science Foundation SBIR-STTR program.

This application claims priority to the following US patent applications:
(a) U.S. Patent Application No. 12/929927, December 23, 2010, "Surface-Controlled Lithium Ion-Exchanging Energy Storage Device," by Aruna Zhamu, CG Liu, David Neff and Bor Z. Jang.
(b) U.S. Patent Application No. 12/930294, "Partially and Fully Surface-Enabled Metal Ion-Exchanging Battery Device," dated January 3, 2011, by Aruna Zhamu, CG Liu, David Neff, Z. Yu and Bor Z. Jang. ”
(c) Aruna Zhamu, CG Liu, Xiqing Wang and Bor Z. Jang, US patent application Ser. No. 13/199450, “Surface-Mediated Lithium Ion-Exchanging Energy Storage Device,” dated August 30, 2011.

  The present invention generally relates to electrochemical energy storage devices, where both the anode and the cathode are lithium into and out of the bulk of the solid electrode active material (ie, no lithium intercalation or deintercalation is required). The present invention relates to a lithium ion exchange energy storage device that is completely comprehensive and does not include diffusion. The lithium storage mechanism at both the anode and cathode is surface controlled, resulting in the need for very slow solid state diffusion (intercalation or deintercalation) of lithium. This device comprises the high energy density of a lithium ion battery and the high power density of a supercapacitor (usually higher than that of the supercapacitor). This device is referred to herein as a surface mediated lithium ion exchange battery device.

Super capacitor (Ultra capacitor or Electrochemical capacitor)
Supercapacitors are being considered for electric vehicles (EV), renewable energy storage and current mesh electrode applications. The high capacity density of supercapacitors is derived from the use of porous electrodes to form large surface areas that contribute to the formation of diffuse double layer charges. This electric double layer (EDL) of charges is formed in the electrolyte near the electrode surface when a voltage is applied. The ions near the electrode required for this EDL mechanism are pre-existing in the liquid electrolyte when the cell is manufactured or in a discharged state and usually do not come from the opposite electrode. In other words, the ions required for EDL formation near the surface of the negative electrode (anode) active material (eg, activated carbon particles) need not come from the anode (cathode), ie, taken up or stored in or on the surface of the cathode active material. Not. Similarly, the ions required for EDL formation near the surface of the cathode active material need not come from the surface or inside of the anode active material.

  When the supercapacitor is recharged, ions already present in the liquid electrolyte (both cations and anions) form an EDL near each electrode (generally due to local molecular or charge ionic polarization). There is no significant ion exchange between the anode active material and the cathode active material. The amount of charge (capacity) that can be stored is defined only by the concentration of cations and anions available in the electrolyte. These concentrations are generally very low (limited by the solubility of the salt in the solvent), resulting in a low energy density. Furthermore, lithium ions are not usually suitable for supercapacitor electrolytes and are not generally used.

  In some supercapacitors, the stored energy is further increased due to pseudo-capacitance effects due to some electrochemical reactions (eg redox reactions). In such a pseudo capacitor, ions contained in the redox pair are preexisting in the electrolyte. Also, there is no significant ion exchange between the anode active material and the cathode active material.

  Since the formation of EDL does not involve chemical reaction or ion exchange between two counter electrodes, the charging or discharging process of an EDL supercapacitor is very fast, typically with a very high power density (typically 5000-10000 W / kg) for a few seconds. Cause it to occur. Compared to batteries, supercapacitors provide higher power density, do not require maintenance, have a long cycle life, require very simple charging circuits, and are generally safer. Physical storage rather than chemical is key to safe operation and very long cycle life.

  Despite the excellent properties of supercapacitors, there are several technical obstacles to the widespread implementation of supercapacitors for various industrial applications. For example, supercapacitors have very low energy density compared to batteries (eg, 5-30 Wh / kg of commercially available supercapacitors versus 10-30 Wh / kg of lead batteries and 50-100 Wh / kg of NiMH batteries. ). Lithium ion batteries generally have a high energy density in the range of 100 to 180 Wh / kg relative to the cell weight.

Lithium-ion batteries Lithium-ion batteries can provide higher energy density but have very low power density (typically 100-500 W / kg) and generally require several hours for recharging. Conventional lithium-ion batteries raise several safety concerns.

  The low power density or long recharge time of the lithium ion battery allows the lithium ions to enter or intercalate into the bulk of the anode active material particles during recharge or into the bulk of the cathode active material particles during discharge. This is due to the required reciprocation of lithium ions between the anode and cathode. For example, as shown in FIG. 1 (A), in the most commonly used lithium ion battery characterized by graphite particles that are anode active materials, lithium ions are graphite at the anode during recharging. It is required to diffuse into the in-plane space of the crystal. Most of these lithium ions need to come frequently from the cathode side by diffusing from the bulk of the cathode active particles through the pores of the solid separator (holes filled with liquid charge) into the bulk of the anode graphite particles. There is.

During discharge, lithium ions diffuse from the anode active material (eg, intercalate from graphite particles), migrate through the liquid electrolyte phase, and then diffuse into the bulk of the composite cathode crystal (eg, lithium cobaltate). , Intercalating into particles of lithium iron phosphate and other lithium insertion compounds). In other words, only the liquid electrolyte reaches the outer upper surface of solid particles (for example, graphite particles having a diameter of 10 μm), and only lithium ions swimming in the liquid electrolyte move to the graphite surface (by fast liquid diffusion). Infiltration of solid graphite particles into the bulk will require slow solid diffusion of lithium ions (commonly referred to as “intercalation”). The diffusion coefficient of lithium in the solid particles of lithium metal oxide is generally 10 ⁻¹⁶ to 10 ⁻⁸ cm ² / second (more generally 10 ⁻¹⁴ to 10 ⁻¹⁰ cm ² / second), and the liquid The diffusion coefficient of lithium in is about 10 ⁻⁶ cm ² / sec.

  In other words, these intercalation or solid state diffusion processes require a long time to achieve because solid state diffusion (or diffusion inside solids) is difficult and slow. This means, for example, that a recharge time is only a few seconds for a supercapacitor, whereas a current lithium ion battery for a plug-in hybrid vehicle requires 2-7 hours. The above suggests that energy storage devices that can store as much as the energy in a battery and can be recharged in 1-2 minutes, such as a supercapacitor, will be considered by innovative advances in energy storage technology. Yes.

More Recent Development Recently, Lee et al. Used multi-walled carbon nanotubes (CNT) containing carbonyl groups as cathode materials for lithium ion capacitors (LIC) containing lithium titanate as an anode material (Non-patent Document 1). . In the half-cell configuration, a relatively high power density is provided by using lithium foil as the anode and functionalized CNT as the cathode. However, CNT-based electrodes prepared by the layer-by-layer (LBL) method have several technical problems that exceed the high cost.
Some of these issues
(1) CNTs are known to contain substantial amounts of impurities, especially transition metal or noble metal particles used as catalysts required for chemical vapor deposition processes. These catalyst materials are not preferred in battery electrodes due to their high tendency to cause harmful reactions to the electrolyte.
(2) CNTs tend to form tangled masses resembling pills that are difficult to operate during electrode manufacture (eg, difficult to disperse in a liquid solvent or resin matrix).
(3) The so-called “layre-by-layer” method (LBL) used by Lee et al. Has mass production or sufficient thickness of battery electrodes (most batteries have electrode thicknesses of 100-300 μm) This is a slow and expensive process that cannot be applied to mass production of electrodes. The thickness of the LBL electrode manufactured by Lee et al. (A famous MIT research group) is limited to 3 μm or less.
(4) It may be wondering how the thickness of the LBLCNT electrode gives performance. Careful inspection of the data provided by Lee et al. (Eg Lee et al. Support material Figure S-7) shows that the power density decreases by an order of magnitude when the LBLCNT electrode thickness is increased from 0.3 μm to 3.0 μm. It is shown that. Even when the electrode thickness increases to the thickness of a useful battery or supercapacitor electrode (e.g., 100-300 [mu] m), performance may be degraded.
(5) Ultrathin LBLCNT electrodes provide high power density (only lithium ions need to travel very short distances), but practical thickness due to insufficient CNT diffusion and electrolyte unreachable problems There is no data to prove that the CNT electrode works. Lee et al. Showed that the CNT composite electrode prepared without using the LBL method did not perform well.
(6) CNTs have a very limited amount of suitable sites that accept functional groups without damaging the bottom structure. CNTs have only one end that is rapidly functionalized, which has a very small ratio to the total surface of the CNT. By chemically functionalizing the outer bottom surface, the electrical conductivity of CNTs is dramatically impaired.

  Most recently, our research group in two patent applications has two new classes of highly conductive cathode active materials with functional groups that can rapidly and reversibly form redox reactions with lithium ions. Reporting the development of These materials are nanographene (single-layer graphene and multilayer graphene sheets generally referred to as nanographene platelets or NGP) and irregular carbon (including soft carbon, hard carbon, carbon black, activated carbon, amorphous carbon, etc.) . These two patent applications are US Pat.

  These novel types of cathode active materials (used in so-called “lithium superbatteries”) can reversibly and rapidly form redox pairs with lithium ions during battery cell charging and discharging cycles. Chemically functionalized nanographene platelets (NGP) or functionalized irregular carbon materials with specific functional groups that can be made. In these two patent applications, functionalized irregular carbon or functionalized NGP is used for the cathode (not the anode) of the lithium superbattery. In this cathode, lithium ions in the liquid electrolyte (at the case of a functionalized NGP cathode) at the edge or surface of the graphene sheet or at the edge / surface of the aromatic ring structure (small graphene sheet) in an irregular carbon matrix I need to move. Solid state diffusion is not required at the cathode. The presence of functionalized graphene or carbon having functional groups therein allows reversible storage of lithium on non-bulk surfaces (including edges) of the cathode material. Such cathode materials provide one type of lithium storage or lithium uptake surface.

In conventional lithium ion batteries, the lithium ions need to diffuse into or out of the bulk of the cathode active material, such as lithium cobaltate (LiCoO ₂ ) and lithium iron phosphate (LiFePO ₄ ). Also, in these conventional lithium ion batteries, the lithium ions need to diffuse into or out of the in-plane space of the graphite crystal that acts as the anode active material. The lithium insertion and extraction process at the cathode and anode is very slow. Due to the slow lithium diffusion process in these intercalation compounds or from the intercalation compounds (commonly referred to as solid state diffusion or intercalation processes), conventional lithium ion batteries cannot deliver high power density and can be recharged. The time required is long. These conventional devices rely on selected functional groups (eg attached to the end or bottom surface of the graphene sheet) that rapidly and reversibly form a redox reaction with lithium ions from the lithium-containing electrolyte. .

  In contrast, a superbattery such as that reported in the two prior applications (Patent Documents 1 and 2) is between a functional group (attached to or bonded to a graphene structure at the cathode) and lithium ions in the electrolyte. Depends on fast and reversible reaction behavior. Lithium ions derived from the anode through only the separator need to diffuse into the liquid electrolyte present in the cathode in order to reach the surface / edge of the graphene surface. These lithium ions need not diffuse into or out of the solid particles. Since diffusion limited intercalation is not included in the cathode, this process is fast and occurs in seconds. Therefore, this is a totally new class of hybrid supercapacitor-battery that exhibits the combined performance of unprecedented and exceptional power density, high energy density, long and stable cycle life, wide operating temperature range It is. This device is the best in both the battery and supercapacitor industries.

In the lithium superbattery described in these two patent applications, the anode is a particle of an anode active material of the lithium titanate type (requiring solid diffusion) conceptually illustrated in FIG. Or only one of the lithium foils (not including the nanostructured material for supporting or incorporating lithium ions / atoms) illustrated in FIG. In the latter case, lithium deposits on the front surface of the anode current collector (eg, copper foil) when the battery is recharged. Since the specific surface area of the current collector is very low (generally 1 m ² / g or less), the overall lithium reprecipitation rate is relatively low (this problem is solved in the present invention).

US patent application Ser. No. 12 / 806,679 US patent application Ser. No. 12 / 924,211 U.S. Patent No. 7,623,340 US Pat. No. 7,745,047 US Pat. No. 7,071,258 US patent application Ser. No. 11 / 800,728

S. W. Lee, et al, “High Power Lithium Batteries from Functionalized Carbon Nanotubes,” Nature Nanotechnology, 5 (2010) 531-537 X. Y. Han et al., “Aromatic carbonyl derivative polymers as high-performance Li-ion storage materials,” Adv. Material, 19, 1616-1621 (2007)

  One embodiment of the present invention is described in U.S. Patent Application No. 12/929927, December 23, 2010, "Surface-Controlled Lithium Ion-Exchanging Energy Storage Device," by Aruna Zhamu, CG Liu, David Neff and Bor Z. Jang. Is disclosed. In this device, at least one of the cathode and anode (not limited to the cathode) comprises a lithium uptake or lithium storage functional surface (generally having a functional group that reacts reversibly with lithium) and both electrodes ( (Not just the cathode) eliminates the need for use in solid state diffusion. This is shown in FIG. 1 (D) and FIG. Both the anode and cathode have a large surface area on which lithium ions are deposited simultaneously, dramatically increasing the charge and discharge rates and increasing the power density. The uniform dispersion of these surfaces of nanostructured materials (eg graphene, CNT, irregular carbon, nanowires, nanofibers) in the electrode is more uniform in the electrode where lithium precipitates more uniformly without forming dendrites. Provide a strong electric field. Such nanostructures eliminate dendritic potential formation, which is a problem in conventional lithium metal batteries (usually used in the 1980s and early 1990s before being replaced by lithium ion batteries). Such an apparatus is referred to herein as a surface controlled lithium ion exchange battery.

  Another embodiment is US Patent Application No. 13/199450, dated August 30, 2011, in which the surface of the anode and the surface of the cathode do not convey a material that yields any functional group capable of forming a redox pair with lithium. Is disclosed. Instead, it is observed that without any functional group, some graphene surfaces can incorporate or confine lithium atoms without the need for solid state diffusion. Regardless of whether the surfaces are equipped with functional groups, graphene surfaces store lithium atoms in a stable and reversible manner where these surfaces can contact lithium ion-containing electrolytes and are in direct contact with the electrolyte. The lithium storage capacity is directly proportional to the total surface area directly exposed to the lithium ion exchange electrolyte, as shown in FIG. For example, the data point with the highest specific capacity in FIG. 13 is a cell with a graphene electrode consisting essentially of all carbon atoms (greater than 98%) without functional groups such as —OH or —COOH. It was a thing. Thus, in this embodiment, the mechanism of the lithium functional group redox reaction may not be a potent lithium storage mechanism.

  In the meaning of the claims of this application, the term “surface-mediated cell” (SMC) refers to any lithium-air (lithium-oxygen) cell, lithium-sulfur cell, or energy storage device operation. It does not include any cell that includes the induction of oxygen from the outside or the formation of metal oxides, metal sulfides, metal selenides, metal tellurides, metal hydroxides or metal halides at the cathode.

The present invention includes (a) an anode (cathode) comprising a functionalized or non-functionalized cathode active material having a surface area for taking up or storing lithium therein, and (b) a function having a surface area for taking up or storing lithium therein. A cathode comprising an activated or non-functionalized anode active material (anode); (c) a porous separator disposed between the two electrodes; and (d) a lithium-containing electrolyte in physical contact with the two electrodes. A surface mediated lithium ion exchange energy storage device (SMC) is provided. In one embodiment, the anode active material and / or the cathode active material has a specific surface area of 100 m ² / g or more that is in direct physical contact with the electrolyte to receive or provide lithium ions thereto. Have

  In one embodiment, at least one of the two electrodes includes a lithium source therein prior to the first charge or first discharge cycle of the energy storage device and at least the cathode active material is not a functionalized material (ie, This material does not have a functional group capable of oxidation-reduction reaction with lithium). The lithium source is preferably in the form of a solid lithium foil, a lithium chip, lithium powder or surface stabilized lithium particles. The lithium source may be a layer of lithium thin film pretreated on the surface of the anode active material.

  In other embodiments, the surface of the SMC electrode material (eg, pure graphene that effectively contains more than 99% carbon) does not have functional groups bonded thereon, and a monolayer of lithium atoms is present in the electrolyte. The lithium ions on the surface can be taken up and stored on the surface in a reversible and stable manner, even if kept immersed in the surface.

  In one embodiment, the electrolyte comprises a liquid electrolyte (eg, an organic or ionic liquid) or gel electrolyte in which lithium ions have a high diffusion coefficient. Solid electrolytes are usually undesirable, but several thin layers of solid electrolyte are used if they exhibit a relatively high diffusion rate.

  In order to explain the operating principle of this battery or storage device (FIG. 2A), a lithium source (eg, a piece of lithium foil) is used to produce a nanostructured anode (eg, a nano-functionalized graphene sheet) when the battery device is manufactured. Non-functionalized so that the nanostructured cathode may be smaller than 2 nm, but preferably surrounded by interconnected pores of nanoscale (2-50 nm) Consider the case with a graphene sheet. Referring to FIGS. 2A-C, during the first discharge cycle, the lithium foil is ionized to produce lithium ions in the liquid electrolyte. Lithium ions move rapidly to the cathode side through the pores of the porous separator. Since the cathode is mesoporous with interconnected pores that accommodate the liquid electrolyte therein, lithium ions basically need to travel through the liquid that reaches the active site on the cathode. In one embodiment, the active site is a functional group in other embodiments and may be the edge or surface of a graphene sheet. In the former case, the subsequent surface oxidation-reduction reaction between the lithium ion and the surface-forming functional group (for example, carbonyl,> = O) is fast and reversible, and in the latter case, the graphene surface directly contacts the electrolyte, and the lithium from the electrolyte Receive ions quickly. Both embodiments allow for fast discharge and high power density of SMC. This is in contrast to conventional lithium ion batteries where lithium ions need to be dispersed in the bulk of solid cathode particles (eg micron sized lithium cobaltate) during discharge, which is a very slow process. .

  In the illustration above, the discharging process is continued until the lithium foil is fully ionized or the active sites on the cathode active material are occupied by lithium atoms. During recharging, lithium ions are released from a large surface of the cathode active material and diffuse through the liquid electrolyte, in one embodiment with or without surface-forming functional groups, and in one embodiment, the anode active material. Incorporated by the surface (eg, simply electrochemically deposited on the surface of the nanostructured anode material). Also, no solid diffusion is required, so the entire process is very fast and the time required for recharging is short. This is in contrast to the required solid state diffusion of lithium ions within the bulk of graphite particles at the anode of a conventional lithium ion battery.

  Clearly, the battery or energy storage device provides a very unique platform for the exchange of lithium ions between the large area of the anode and the large area of the cathode that does not require solid state diffusion at both electrodes. This step is substantially required by the surface uptake of lithium ions + liquid phase diffusion (all very fast). This device is therefore referred to herein as a surface mediated lithium ion exchange battery. This is entirely different from conventional lithium ion batteries, which require solid state diffusion (intercalation and deintercalation) of lithium at both the anode and cathode during charge and discharge cycles, and energy storage devices. Are clearly different classes.

  This surface-mediated lithium ion exchange battery device is clearly different from conventional supercapacitors based on an electric double layer (EDL) mechanism or a pseudo-capacitance mechanism. In both mechanisms, lithium ions are not exchanged between the two electrodes (since lithium is not stored in the electrode bulk or surface, but instead is stored in an electric double layer near the electrode surface). When the supercapacitor is recharged, an electric double layer is formed near the activated carbon surface on both sides of the anode and cathode. Each and all of the EDLs consist of a layer of negatively charged species and a layer of positively charged species (in addition to the charge on the surface of the electrode material (eg, activated carbon)). When the supercapacitor is discharged, both negatively charged species and positively charged species are randomized in the electrode (further away from the electrode material surface). In contrast, when the SMC is recharged, substantially all of the lithium ions are incorporated or electroplated on the surface of the anode active material and the cathode side is substantially free of lithium. When the SMC is discharged, substantially all of the lithium ions are taken up by the cathode active material surface (stored in the defect and bonded to the benzene ring center or react with the functional group). Very little lithium remains in the electrolyte.

  Significantly, in conventional supercapacitors, the charge storage capacity of the supercapacitor (even when using a lithium-containing electrolyte) is limited by the amount of cations and anions involved in the formation of EDL charge. These amounts are defined by the original concentration of lithium ions and counter ions (anions) derived from the lithium salt defined by the limiting solubility of these ions in the electrolyte solvent. To illustrate this point, assume that up to 1 mole of lithium ion can be dissolved in 1 mL of solvent, and a total of 5 mL of solvent added to a particular supercapacitor cell. Then, the maximum amount of lithium ions present in the entire cell is 5 mol, and this amount defines the maximum amount of charge that can be stored in this supercapacitor.

  On the other hand, the amount of lithium ions reciprocating between the anode surface and the cathode surface of the SMC is not limited by the chemical solubility of the lithium salt in the same solvent. Assume that the same 5 mL of solvent (containing 5 moles of lithium ions as described in the supercapacitor above) was used for SMC. Since the solvent is already fully saturated with the lithium salt, it will be expected that this solvent will or will not accept additional lithium ions from the lithium source (5 moles is the maximum). Thus, these 5 moles of lithium ions are the maximum amount of lithium we use for charge storage (ie, the maximum amount of lithium ions that can be taken up by the cathode during discharge or the lithium ions that can be taken up by the anode during recharging). Would be expected to be the maximum amount). Contrary to this expectation by those skilled in the field of electrochemistry or very ordinary engineers, surprisingly, the amount of lithium ions taken up by the electrode surface in the SMC (or the amount of lithium ions reciprocated between the two electrodes) We have found that) is one or two orders of magnitude greater than this solubility. The introduction of a lithium source at this anode seems to ignore this expectation by dramatically providing more lithium ions than the solvent dissolves there.

  More surprisingly, in SMC, the amount of lithium that can contribute to charge storage is controlled (limited) by the amount of surface active sites on the cathode from which lithium ions can be taken from the electrolyte. This is because the introduced lithium source can supply an excess amount of lithium ions even when the amount of surface active sites is greater than the amount of lithium ions that the solvent can hold at one time (eg, 5 moles in this discussion). Because. As described above, in one embodiment, these active sites are functional groups or graphene surface defects or benzene ring centers on the graphene surface (FIGS. 3D and 3E). Surprisingly, it was found that lithium atoms are strongly and reversibly bound to the individual centers of the benzene rings (carbon hexagons) that make up the graphene sheet, or are reversibly confined by graphene surface defect sites. It was.

The surface-mediated lithium ion exchange battery device is a super battery as disclosed in our two prior applications (Patent Documents 1 and 2) that do not include an anode active material in the anode (the anode side includes only the anode current collector). Is clearly different. In the energy storage device of the present invention, not only the cathode, but also the anode has a large surface area on which lithium ions can simultaneously precipitate, allowing for dramatically higher charge and discharge rates and high power density. In other words, in a high current density state (during fast recharge), a large amount of lithium ions is quickly filled on the anode side looking for a site where each lithium ion precipitates or reacts. The anode current collector (eg, copper foil) has a small surface area available at a time and cannot control such high flow rates of lithium ions. In contrast, the large specific surface area of the nanostructured anode and optically functionalized material (eg, graphene or CNT or functionalized product thereof) can simultaneously modulate lithium ions in large quantities. Also, the uniform dispersion of the nanomaterial (eg, graphene or CNT) in the electrode on these surfaces provides a more uniform electric field in the electrode where lithium precipitates more uniformly without forming dendrites. This means that the larger the surface area, the more precipitation spots, each with less lithium, which is insufficient to form dangerous dendritic crystals.
Such nanostructures eliminate the potential dendritic formation that was the most serious problem in conventional lithium metal batteries.

In one embodiment of this SMC device, at least the cathode of the two electrodes has an active material that is not a functionalized material (ie, there are no functional groups provided on the surface exposed to the electrolyte). The term “functionalized material” means a material having a functional group (eg, carbonyl group) that can react with a lithium atom or ion forming a redox pair. The cathode active material has a high specific surface area (greater than 100 m ² / g) in direct contact with the electrolyte (eg, directly immersed in the electrolyte), takes up lithium ions from the electrolyte, reacts with the lithium ions, and surface active sites Lithium atoms can be stored in (eg surface defects or benzene ring centers).

Both electrodes preferably have a high specific surface area (greater than 100 m ² / g) and can be in direct contact with the electrolyte and take up / store lithium ions in the surface active sites. At least one of the two electrodes is 500 m ² / g or more (preferably more than 1000 m ² / g, more preferably more than 1500 m ² / g, even more preferably, for storing or supporting lithium ions or atoms therein. Preferably includes a nanostructured non-functionalized material having a high specific surface area of greater than 2000 m ² / g).

  The lithium source preferably includes a lithium chip, lithium foil, lithium powder, surface passivated or stabilized lithium particles, or combinations thereof. The lithium source may be immersed on the anode side before the first discharge process is performed on the battery device. Alternatively, the lithium source may be immersed on the cathode side before the first charging step is performed on this battery device. Still further, the cathode and anode may be assembled to include several lithium sources during the battery manufacturing process. It is important that this solid lithium source supplies most of the lithium ions that are exchanged between the anode and cathode surfaces during the charge-discharge cycle. Naturally, many of the lithium ions that require lithium-containing electrolytes are provided, but this amount is too small for battery devices that achieve high energy density. This is because, even if a lithium-based electrolyte is provided, a symmetrical capacitor does not exhibit a high energy density.

In one embodiment of the SMC device, at least one (preferably both) of the anode active material and the cathode active material is selected from:
(A) a porous irregular carbon material selected from soft carbon, hard carbon, polymerizable carbon or carbonized resin, mesofuse carbon, coke, carbonized pitch, carbon black, activated carbon or partially graphitized carbon;
(B) Graphene selected from graphene single-layer sheets or multilayer platelets, graphene oxide, graphene fluoride, graphene hydroxide, graphene nitride, boron-doped graphene, nitrogen-top graphene, or chemically or thermally reduced graphene oxide material,
(C) Exfoliated graphite,
(D) mesoporous carbon (eg obtained by template-assisted synthesis or chemical activation of mesophase carbon),
(E) a carbon nanotube selected from single-walled carbon nanotubes or multi-walled carbon nanotubes,
(F) carbon nanofibers, metal nanowires, metal oxide nanowires or fibers, or conductive polymer nanofibers,
(G) These combinations.

  Although CNTs are not suitable nanostructured materials due to high cost and other technical issues, CNTs nevertheless (alone or in combination with other nanostructured materials) are still used in the surface-controlled lithium ion exchange battery of the present invention be able to.

In embodiments having functional groups on one or both of the anode and cathode, representative materials are poly (2,5-hydroxy-1,4-benzoquinone-3,6-methylene), Li _x C ₆ O _6. (X = 1 to 3), Li ₂ (C ₆ H ₂ O ₄ ), Li ₂ C ₈ H ₄ O ₄ (Li terephthalate), Li ₂ C ₆ H ₄ O ₄ (Li trans-trans-muconate), 3 , 4,9,10-perylenetetracarboxylic dianhydride (PTCDA) sulfide polymer, PTCDA, 1,4,5,8, -naphthalene-tetracarboxylic dianhydride (NTCDA), benzene-1,2, It is selected from the group of 4,5-tetracarboxylic dianhydride, 1,4,5,8-tetraanhydroanthraquinone, tetraanhydro-p-benzoquinone and combinations thereof. In one embodiment, at least one functional material, R is a hydrocarbon (e.g. 1 to 6 carbon _{atoms), -COOH, = O, -NH} 2, -OR, -COOR, combinations thereof Having a functional group selected from a group. These organic or polymerizable materials (molecules or salts) have a functional group (for example, a carbonyl group) that can perform a reversible and rapid redox reaction with lithium. These functional groups tend to have relatively low electrical conductivity, and therefore functional groups selected from this group (for example, nanostructured materials such as nanographene, carbon nanotubes, disordered carbon, nanographite, and , Nanographene, carbon nanotubes, irregular carbon, nanographite, metal nanowires, conductive nanowires, carbon nanofibers, those that are chemically bonded or attached to a material selected from polymerizable nanofibers) . For example, an aromatic ring constituting graphene and irregular carbon (soft carbon, hard carbon, activated carbon, carbon black, etc.) and a functional group bonded on the functionalized material (for example, hydroxyl group of tetrahydroxy-p-benzoquinone) It has a functional group capable of reacting at its end or surface.

  Alternatively, nanostructured carbon materials such as non-functionalized nanographene, carbon nanotubes, disordered carbon or nanographite may simply provide a surface on which lithium atoms are deposited, for example, by confined defect sites or by incorporating benzene ring centers. Good. Even in the absence of reactive functional groups, the presence of nanostructured material provides a wide lithium storage surface.

  In one embodiment, the irregular carbon material is formed from two layers, a first phase that is a stack of graphite crystals or graphene surfaces and a second phase that is amorphous carbon, the first phase being in the second phase. It may be dispersed or combined by a second phase. The irregular carbon material may comprise less than 90% by weight of graphite crystals and at least 10% by weight of amorphous carbon.

  The SMC anode or cathode active material may comprise non-functionalized nanographene selected from single layer graphene sheets or multilayer graphene platelets. Alternatively, the active material may comprise single-walled or multi-walled carbon nanotubes.

  Thus, in one embodiment of the present invention, the anode active material and / or cathode active material of SMC is graphene, graphene oxide, graphene fluoride, graphene hydroxide, graphene nitride, boron-doped graphene, nitrogen-doped graphene, Doped graphene or a non-functionalized graphene material selected from chemically or thermally reduced graphene oxide monolayer sheets or multilayer platelets. Alternatively, the anode active material and / or cathode active material can be non-functionalized single-walled or multi-walled carbon nanotubes (CNT), oxidized CNT, fluorinated CNT, hydroxylated CNT, nitrided CNT, boron-doped CNT, nitrogen-doped CNT or doped. CNT.

The lithium source can be lithium metal (eg, a thin foil or powder, preferably stabilized or surface passivated), lithium metal alloy, lithium metal or a mixture of lithium alloy and lithium intercalation compound, lithium treatment compound, It may be selected from lithium-treated titanium dioxide, lithium titanate, lithium manganate, lithium transition metal oxide, Li ₄ Ti ₅ O ₁₂ , or combinations thereof. The lithium intercalation compound or the lithium treatment compound may be selected from the following group of materials. Specifically, the lithium intercalation compound or the lithium treatment compound may be selected from the following material group.
(A) Lithium-treated silicon (Si), lithium-treated germanium (Ge), lithium-treated tin (Sn), lithium-treated lead (Pb), lithium-treated antimony (Sb), lithium-treated bismuth (Bi), lithium-treated zinc (Zn) ), Lithium-treated aluminum (Al), lithium-treated titanium (Ti), lithium-treated cobalt (Co), lithium-treated nickel (Ni), lithium-treated manganese (Mn), lithium-treated cadmium (Cd) and combinations thereof,
(B) a lithium-treated alloy or intermetallic compound of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd and mixtures thereof;
(C) Lithium treated oxides, carbides, nitrides, sulfides, phosphides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd and mixtures thereof Selenides, tellurides or antimonides or combinations thereof,
(D) A lithium-treated salt or hydroxide of Sn.

  The electrolyte may be selected from any electrolyte used in conventional lithium ion batteries or lithium metal batteries. The electrolyte is preferably a liquid electrolyte or a gel electrolyte. The charge material may comprise a lithium salt doped ionic liquid. In the battery device, the anode preferably has a thickness of more than 5 μm, preferably more than 50 μm, more preferably more than 100 μm.

  In one embodiment, at least 90% of the lithium in the SMC is stored on the surface of the anode active material (lithium is in physical contact with the anode surface) when the device is charged and the device is discharged In this case, it is stored on the surface of the cathode active material (lithium is in physical contact with the cathode surface).

  SMCs typically operate in the 1.0 to 4.5 volt range, but are expected to operate in a subset of this range (eg, 1.5 to 4.0 volts or 2.0 to 3.9 volts, etc.). It may be specified. It may operate (though not preferred) above 4.5 volts or below 1.0 volts. Symmetric supercapacitors featuring organic electrolytes can operate up to 3.0 volts, but generally operate from 0 to 2.7 volts. On the other hand, SMCs using exactly the same organic electrolyte generally operate at 1.5 to 4.5 volts. This is another evidence that SMCs and supercapacitors are two fundamentally different classes of energy storage devices that operate with different mechanisms and principles.

  SMC charging and / or discharging operations do not include lithium intercalation or solid state diffusion. This is the normal case even if multilayer graphene platelets are used for either the anode or the cathode. Lithium intercalation between the two graphene planes occurs (in proportion to lithium / lithium ions) below 1.5 volts, preferably below 0.3 volts. The lithium ion exchange cell of the present invention includes a reciprocation of lithium ions between the anode and cathode surfaces operating in the range of 1.5 to 4.5 volts.

  Quite surprisingly, SMC devices generally provide an energy density of 150 Wh / kg or higher and a power density of 25 Kw / kg or higher relative to the total electrode weight. More generally, battery devices provide an energy density greater than 300 Wh / kg and a power density greater than 20 Kw / kg. In many cases, battery devices provide energy densities greater than 400 Wh / kg and power densities greater than 10 Kw / kg. Most commonly, battery devices provide an energy density greater than 300 Wh / kg or a power density greater than 100 Kw / kg. In some cases, the power density is significantly higher than 200 Kw / kg, even higher than 400 Kw / kg, and 1-3 orders of magnitude higher than the power density of conventional supercapacitors (1-10 Kw / kg).

  In SMC, the anode preferably has a thickness of more than 5 μm, preferably more than 50 μm, more preferably more than 100 μm.

  The present invention also provides a method of operating an energy storage device (SMC). The method includes providing a lithium source at the anode and ionizing the lithium source to release lithium ions into the electrolyte during the first discharge cycle of the device. The method further includes the step of electrochemically inducing lithium ions released on the cathode and taking in the lithium ions released by interacting with the cathode active material, eg, functional groups or graphene. In addition, the method includes the steps of releasing lithium ions from the cathode surface during the device recharge cycle and electrochemically inducing lithium ions released to the anode active material surface using an external battery charger. .

  Alternatively, the method may comprise providing a lithium source at the cathode and operating the lithium source to release lithium ions into the electrolyte during the initial charge cycle of the device.

  The invention includes (a) providing a surface intervening cell comprising an anode, a lithium source, a porous separator, a liquid or gel electrolyte and a cathode; and (b) lithium ions from the lithium source during the initial discharge of the device. And (c) exchanging lithium ions between the lithium uptake surface of the anode and the lithium uptake surface of the cathode during successive charging or discharging, and in one embodiment the anode And / or the cathode is functionalized, and in a second embodiment further provides a method of operating a surface mediated energy storage device, wherein the anode and / or cathode is a non-functionalized material having a lithium uptake surface. It is preferred that both charging and discharging of the device do not involve lithium intercalation or solid state diffusion.

The present application discloses another method of operation of a surface mediated energy storage device. This method consists of (a) providing a surface intervening cell comprising an anode, a lithium source, a porous separator, an electrolyte (containing an initial amount of lithium ions) and a cathode, and (b) during the initial discharge of the device. A step of releasing lithium ions into the electrolyte from the lithium source; and (c) taking in lithium ions from the electrolyte at the cathode (over 100 m ² / g, more preferably over 1000 m ² / g, and even more preferably over 2000 m ² / g. Storing lithium incorporated on the cathode surface (having a specific surface area of greater than), and (d) between the lithium uptake surface of the anode and the lithium uptake surface of the cathode during successive charge or discharge operations ( Exchanging lithium ions (greater than the initial amount) and both the anode and cathode are in contact with the electrolyte They comprise a material having lithium uptake surface that, the charging operation does not contain lithium infiltration.

(A) is a conventional lithium ion battery cell using graphite, Si or lithium titanate as the anode active material and lithium iron phosphate (or lithium cobaltate) as the cathode active material. (B) is a conventional lithium super battery having a cathode made of lithium titanate and a functional material (for example, functionalized nanographene, CNT or irregular carbon powder) as an anode active material. (C) is a lithium foil anode conventional lithium super battery cell (with no nanostructured functional material) and a lithium foil anode with a cathode made of functionalized graphene, CNT or irregular carbon. (D) is a nanostructured material (with or without a functional group capable of reacting with lithium ions or atoms), a lithium source (for example, lithium foil or surface non-conductive lithium powder), a porous separator, a liquid Or an example of a surface mediated lithium ion exchange battery device that is an embodiment of the present invention comprising a gel electrolyte (preferably in solution), a nanostructured functional material at the cathode.

(A) is a nanostructured material at the anode, a lithium source (eg, lithium foil or surface stabilized lithium powder), a porous separator, a liquid electrolyte, and a nanostructured nonfunctionalized material at the cathode (first discharge or charge cycle) The structure of the surface-mediated lithium ion exchange battery device in front of FIG. (B) shows the structure of this battery device after the first discharge operation (lithium is ionized, lithium ions diffuse in the liquid electrolyte and reach the surface of the nanostructure cathode (functionalized or nonfunctionalized). Is taken up more rapidly by the surface). (C) shows the structure of this battery device after recharging (lithium ions are released from the cathode surface, diffuse in the liquid electrolyte, and reach the surface of the nanostructured anode (functionalized or nonfunctionalized). Quickly coat the top). The large surface area acts as a support substrate on which a large amount of lithium ions are electrodeposited simultaneously. Such simultaneous mass deposition cannot be achieved with an anode current collector having a low specific surface area.

(A) is a schematic diagram of a lithium storage mechanism in which an aromatic ring or a functional group bonded to the end or surface of a graphene sheet can rapidly react with lithium ions to form a redox pair. (B) is a theoretical structural formula of an electric double layer that is a minor or minor mechanism of charge storage. (C) is lithium taken into the center of the benzene ring on the graphene surface. (D) is a lithium atom confined in a graphene surface defect.

2 is an illustration of disordered carbon used as a nanostructured material having a high specific surface area (in direct contact with the electrolyte) at the anode and / or cathode. (A) is a schematic view of soft carbon in which adjacent stacks of graphene sheets or small aromatic rings face each other at a small angle for growth or bonding (graphitization). (B) is (non-graphitized) hard carbon. (C) is a carbon black with a large amount of small aromatic ring domains arranged to form nanoscale spherical particles. Preferably, as shown in (D), the individual carbon black particles are activated so that the liquid electrolyte spreads a small gate in order to access the edges or surface functional groups inside the particles.

(A) is a scanning electron microscope image of a curved nano graphene sheet. (B) is a scanning electron microscope image of another graphene form. These graphene forms provide a very high specific surface area (generally 300-2000 m ² / g).

(A) is a Ragone plot of 5 types of cells: two surface mediated lithium ion exchange battery cells (one with functional groups on both electrode active materials and the other with non-functionalized active materials), Conventional lithium super battery (with lithium metal anode and functionalized irregular carbon cathode), conventional symmetrical supercapacitor with two functionalized irregular carbon electrodes (without lithium foil as lithium source), Symmetric supercapacitor based on LBL-CNT (CNT supercapacitor data can be read from Lee et al.). (B) is an energy density value plotted as a correlation of the number of charge / discharge cycles for a functionalized surface cell and a non-functionalized SMC.

(A) is a Lagone plot of a functionalized NGP-based lithium superbattery and two corresponding surface-mediated lithium ion exchange battery devices, one with functional groups and the other with no functional groups. These data further indicate that the surface mediator works better than the super battery, especially at high density (high power region). (B) is the long-term cycle stability of SMC in one embodiment of the present invention relative to that of prior art SMC (having functional groups in the electrode).

(A) is a charge / discharge curve of three surface capable cells (cell M is NGP derived from graphite, cell C is NGP derived from carbon fiber, and cell G is exfoliated graphite EG). The discharge current density is 1 A / g. (B) is a CV plot of the same cell at a scan rate of 25 mV / s. (C) is a lagone plot of these cells with a thick cathode (200 μm). (D) is a lagone plot of NGP, CB (carbon black), t-CB (chemically treated CB) and AC-based surface mediated cells with thick cathodes. All energy density and power density values are cell level values calculated based on the total cell weight.

FIG. 2 is a cycle voltammetry (CV) diagram of a corresponding surface mediated cell (right curve) of the present invention with a graphene-based symmetric supercapacitor (left curve) and a lithium source supplied to the anode.

FIG. 4 is a Lagone plot of graphene surface capable lithium ion exchange cells with different electrode thicknesses. Energy density and power density values were calculated based on total cell weight (A) and cathode weight only (B).

Cycle performance of several SMCs: cell N (chemically reduced graphene system), cell AC (activated carbon) and cell M (exfoliated graphite derived from artificial graphite).

Specific capacity plotted as correlation of electrode specific surface area for several cells. The electrodes were prepared from different graphene-based materials.

  The invention will be more readily understood by reference to the following detailed description of the invention, taken in conjunction with the accompanying drawings, which form a part of this disclosure. It is to be understood that the present invention is not limited to the specific apparatus, methods, conditions, or parameters described and / or shown herein, and that the terminology used herein is for the specific embodiments described through examples only. It will be understood that there is no intention to limit the claimed invention.

  The present invention provides an electrochemical energy storage device called a surface mediated lithium ion exchange cell (or simple surface mediated cell SMC). In many embodiments, the SMC device is significantly higher than the power density of a conventional supercapacitor and provides a power density that is dramatically higher than that of a conventional lithium ion battery. This device corresponds to that of a battery and exhibits a significantly higher energy density than conventional supercapacitors.

  A surface mediated ion exchange battery is a functionalized or nonfunctionalized material having a lithium storage or lithium uptake surface (functionalized or nonfunctionalized material may be a nanostructure having nanoscale or mesoscale pores and a large surface area. A cathode comprising a high surface area material (preferably a nanostructure having nanoscale or mesoscale pores) having a lithium storage or lithium uptake surface, and a porous separator disposed between the two electrodes A lithium-containing electrolyte in physical contact with the two electrodes and a lithium ion source supplied at the anode or cathode. These lithium uptake surfaces are in direct contact with the electrolyte from which they take up or release lithium ions. Although it may be chosen to use an aqueous or solid electrolyte, suitable electrolyte types are organic liquid electrolytes, gel electrolytes, ionic liquid electrolytes (preferably containing lithium ions) or combinations thereof .

The lithium ion source is selected from a lithium chip, lithium foil, lithium powder, surface-stabilized lithium particles, a lithium film coated on the surface of the anode or cathode active material, or combinations thereof. In a preferred embodiment, the anode active material is pre-treated with lithium or pre-coated or plated with lithium. As a lithium source, in addition to relatively pure lithium metal, lithium metal alloy, lithium metal or a mixture of lithium alloy and lithium intercalation compound, lithium treatment compound, lithium treatment titanium dioxide, lithium titanate, lithium manganate , Lithium transition metal oxide, Li ₄ Ti ₅ O ₁₂ , or combinations thereof. The lithium intercalation compound or the lithium treatment compound may be selected from the following group of materials. (A) Lithium-treated silicon (Si), lithium-treated germanium (Ge), lithium-treated tin (Sn), lithium-treated lead (Pb), lithium-treated antimony (Sb), lithium-treated bismuth (Bi), lithium-treated zinc (Zn) ), Lithium-treated aluminum (Al), lithium-treated titanium (Ti), lithium-treated cobalt (Co), lithium-treated nickel (Ni), lithium-treated manganese (Mn), lithium-treated cadmium (Cd) and combinations thereof; (b ) Li-treated alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd and mixtures thereof; (c) Si, Ge, Sn, Pb, Lithium treatment of Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd and mixtures thereof. Oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides or antimonide, or combinations thereof; (d) Sn lithium treatment salt or hydroxide.

  The electrode thickness is not limited, but the anode preferably has a thickness of more than 5 μm, preferably more than 50 μm, more preferably more than 100 μm. An example of such a surface-mediated ion exchange battery device is shown in FIG. 1 (D) and FIG.

  Although not wishing to be bound by any theory, the following theoretical considerations are probably useful.

The internal structure of a conventional lithium ion battery is schematically shown in FIG. In the battery discharged state, the lithium ions, graphite, silicon, diffusion from the bulk of the anode active material such as lithium titanate (particle diameter = d _a and the average solid diffusion length = d a _{/ 2)} (deintercalating) And move across the anode thickness (anode layer thickness = La and average diffusion distance = La / 2) into the liquid electrolyte. Subsequently, the lithium ions move (into the liquid electrolyte) across the porous separator (thickness) = Ls) and reach the spherical cathode active material particles (average diffusion distance = Lc / 2). the cathode thickness in (thickness = Lc) diffuses across a portion of, then particles diffuse into the bulk of the (diameter = d _c and required average solid diffusion length = d c _{/ 2)} (intercalated) To do. In the recharged state, lithium ions move approximately the same distance in the opposite direction.

  In other words, the operation of a conventional lithium ion battery involves intercalating lithium ions from the bulk (not the surface) of electrode active material particles in one electrode (eg, the anode during discharge) and the opposite electrode (eg, Intercalating lithium ions into the bulk of the electrode active material particles at the cathode). In general, diffusion in liquid electrolytes is fast, but diffusion in solids is dramatically slow (3-8 orders of magnitude). The surface mediated cell (SMC) of the present invention essentially works for the exchange of large amounts of lithium ions between porous electrode surfaces (not in the bulk of the electrode as in a lithium ion battery). This method completely eliminates the need for time consuming steps of lithium intercalation and deintercalation. SMC essentially does not intercalate, and the majority of lithium is stored on the large surface area of the electrode active material particles. Generally, more than 90% of the lithium atoms are incorporated on the graphene surface, and more typically less than 1% of the lithium happens to enter the multilayer graphene structure. The charge / discharge time of SMC, which is very fast and very high power density, not even comparable with supercapacitors (famous for high power density), is that of lithium ions in the liquid electrolyte (organic or ionic liquid) Limited only by movement. This will be further described below.

と推定される。なお、Ｄ_{ｅｌｅｃｔｒｏｌｙｔｅ}＝電解質中のリチウムイオン拡散係数であり、Ｄ_ａ＝アノード活性材料粒子中のリチウムイオン拡散係数であり、Ｄ_ｓ＝多孔性セパレータを通過するリチウムイオン拡散係数であり、Ｄ_ｃ＝カソード活性材料粒子中のリチウムイオン拡散係数である。 Assuming that the diffusion coefficient of lithium ions in the particle medium is D and the required moving distance is x, the required diffusion time is estimated as t˜x ² / D according to a known kinetic equation. As an approximate linear equation, the total time scale required to complete the lithium ion charge or discharge process is:

It is estimated to be. _Where D _electorite = lithium ion diffusion coefficient in the electrolyte, D _a = lithium ion diffusion coefficient in the anode active material particles, D _s = lithium ion diffusion coefficient passing through the porous separator, and D _c = It is a lithium ion diffusion coefficient in the cathode active material particles.

Typical diffusion coefficients for lithium ions in various liquid media or solid films or particles are listed below (based on open literature data). Liquid electrolyte (2 × 10 ⁻⁶ cm ² / s), separator (7.5 × 10 ⁻⁷ cm ² / s), LiFePO ₄ cathode (10 ⁻¹³ cm ² / s), Li ₃ V ₂ (PO ₄ ) ₃ cathodes (10 ⁻¹³ to 10 ⁻⁹ cm ² / s), nano-Si anodes (10 ⁻¹² cm ² / s), graphite anodes (1 to 4 × 10 ⁻¹⁰ cm ² / s) and Li 4 Ti 5 O 12 anodes (1. 3 × 10 ⁻¹¹ cm ² / s). This is because in the conventional lithium ion battery cell in which LiFePO ₄ particles are used as the cathode active material, the last term in formula (1): (d _c / 2) ² / D _c is due to a very low diffusion coefficient. It shows that it dominates the total diffusion time required. Actually, the value of the diffusion coefficient is 10 ⁻¹⁰ to 10 ⁻ depending on the lithium content in the Li _x FePO ₄ and Li _1-x FePO ₄ (x is less than 0.02) solid solution or the LiFePO ₄ / FePO ₄ phase ratio. It varies between ¹⁶ cm ² / s.

In contrast, a mesoporous cathode of functionalized nanocarbon material (eg graphene, CNT or irregular carbon) and a lithium metal foil as the anode (shown conceptually in FIG. 1C) In a superbattery (partial surface mediated cell), lithium ions do not need to diffuse through solid cathode particles, so a low solid diffusion coefficient at the cathode (eg, 10 ⁻¹³ cm ² in LiFePO ₄ particles). / S). On the contrary, since the cathode active material is highly porous, lithium ions that pass through a liquid medium (not a solid medium) having a high diffusion coefficient (eg 2 × 10 ⁻⁶ cm ² / s) and diffuse into the pores In order to react rapidly and reversibly, the electrolyte can reach the inside of the pore where the functional group exists. In such a super battery, the last term in equation (1): (d _c / 2) ² / D _c is virtually absent. The total diffusion time required is defined by the electrode and separator thickness. The above consideration is based on the premise that the reversible reaction between the functional group in the electrolyte and the lithium ion is fast, and the entire charge / discharge process is not controlled.

  In a conventional lithium ion capacitor (LIC), the cathode is a mesoporous structure of a nanocarbon material (eg, activated carbon), but lithium titanate or graphite particles (conceptually shown in FIG. 1B). Configure the anode. In the cell discharge state, lithium ions diffuse from the lithium titanate particles or graphite particles (slow deintercalation step) and move across the anode thickness into the liquid electrolyte. Subsequently, lithium ions migrate across the porous separator (into the liquid electrolyte), diffuse across a portion of the cathode thickness in the liquid electrolyte, and in a position close to the surface area of the nanostructured cathode active material. To reach. There is no need for solid diffusion at the cathode. The entire process is essentially defined by the solid state diffusion at the anode. Thus, this LIC will exhibit a slower kinetic process (low power density) compared to a superbattery (partial surface mediation) and the full surface mediation cell (SMC) disclosed herein.

By using representative values of various parameters in equation (1), the total lithium transfer required for battery charging or discharging processes in some conventional lithium ion battery types and some conventional super battery cells and LICs. We get time. The first group is a conventional lithium ion battery (Gr / LiFePO ₄ ) with a graphite particle anode and a lithium iron phosphate cathode. The second and third groups are conventional lithium ion batteries (nano) Si / LiFePO ₄ and Li ₄ Ti ₅ O ₁₂ / LiFePO ₄ ) with LiFePO ₄ cathodes and Si particles or lithium titanate anodes, respectively. is there. The fourth group is LIC (Li ₄ Ti ₅ O ₁₂ / f-CNM) in which the anode is composed of Li ₄ Ti ₅ O ₁₂ particles and the cathode is a functionalized cathode nanomaterial such as CNT or activated carbon (AC). . The fifth group is a partial surface mediated cell (Li foil / f-CNM) where the anode is a lithium foil and the cathode is a carbon nanomaterial. These data are shown in Tables 1 and 2 below.

Some notable results are obtained from the data in Tables 1 and 2.
(1) A conventional lithium ion battery (first group) including a microsize graphite particle anode (graphite diameter = 20 μm) and a microsize LiFePO ₄ cathode (particle size = 1 μm) is a necessary lithium ion diffusion step. It will take several hours (eg 8.4 hours) to complete. This is because conventional lithium ion batteries exhibit very low power density (typically 100-500 W / Kg) and very long recharge times.
(2) This long diffusion time problem is partially alleviated by using nanoscale particles, as in the second and third groups above (eg, anode and cathode active material particles have a particle size of 100 nm). 8 minutes if you have).
(3) In contrast, in a LIC equipped with a carbon cathode (eg, f-CNT) and an anode of Li ₄ Ti ₅ O ₁₂ nanoparticles, the required diffusion time is 235 seconds (4 Min.) To 1.96 seconds with ultra-thin cathodes (eg 0.3 μmL BLf-CNTs prepared by the MIT research group's layer-by-layer method (Non-Patent Document 1)). Unfortunately, such ultra-thin electrodes (0.3-3 μm) are of very limited utility value.
(4) In the lithium super battery (partial surface mediation), the electrode thickness is a dominant factor. For example, when lithium metal foil is used as the anode (first type), the total diffusion time is short (less than 0.6 seconds when the cathode thickness is 0.3 μm or 3 μm), but when the cathode thickness is 200 μm Increase to 103 seconds (less than 2 minutes).
(5) The above results show that the lithium super battery will have an abnormal power density, especially when the electrodes are ultra-thin. This is the reason why MIT Lee et al. Reported that the power density in a lithium super battery with a 0.3 μm thick LBLf-CNT cathode was 100 Kw / Kg. However, useful electrode sizes are at least 50 μm thick (typically 100-300 μm), and cells having a cathode thickness of 0.3-3.0 μm have very limited practical utility values. . The very high power density obtained in the lithium superbattery with LBLf-CNT cathode reported by Lee et al. Is due to the ultra-thin cathode thickness (0.3 μm).

  As shown in FIG. 11, our graphene-based surface mediated cells (which typically have an electrode thickness of 100-300 μm) perform better than thin electrode-based LBLf-CNT cells (partial surface mediated) .

  It should be noted that the above calculations for a superbattery that includes a lithium foil as the anode are well applicable to the surface-mediated energy storage device of the present invention, except that the lithium foil thickness is replaced with the nanostructure anode thickness. Because the nanostructured anode is “elastic” or compressible, the lithium source (lithium particles or pieces of lithium foil) will not add additional anode thickness values to the time calculation. The lithium foil may be compressed against the nanostructured anode, and the lithium particles may be incorporated into the nanostructured anode during battery device fabrication. If the lithium particles or foil are ionized during the first discharge cycle, the nanostructured anode (eg, NGP or CNT-based mat) will quickly return to contact the separator.

In addition, in the lithium super battery (Li foil / f-CNM) in which the anode is a lithium foil, there is no anode particle, and therefore there is no particle size (d _a is set to zero in the above calculation). During the first discharge, the lithium foil is electrochemically ionized and releases ions. In the above calculations, this surface control reaction is considered fast and not rate limiting. In fact, this surface reaction is rate limiting when a high discharge rate is required (ie when an external circuit or load requires high current density). This limitation is not controlled by the surface ionization rate, but is controlled by the limited surface area of the lithium foil during the first discharge cycle. In other words, it has a surface area such that lithium ions are released simultaneously at a predetermined time during the first discharge cycle.

During the recharge cycle, lithium ions migrate from the cathode to the anode side and re-apply on the surface of the anode current collector (eg copper foil), which is the surface available at the anode of the superbattery (partial surface mediator cell). Precipitate. There are two problems with using a current collector (eg, copper foil) alone to control the inflow of large amounts of lithium ions during recharging.
(1) When the recharge rate is fast (having a high circuit current density), a large amount of lithium ions that move rapidly to the anode side are generally very low in surface area (generally, the specific surface area of copper foil is 1 m ² / g or less. Try to deposit on the surface of the current collector with This limited surface area becomes the rate limiting for precipitation.
(2) When the recharge rate is slow (has a low current density), lithium ions are turned back and the deposition on the current collector surface becomes non-uniform. Some advantageous spots accept deposited lithium atoms faster, and these spots continue to deposit at high speed. Such non-uniform lithium deposition results in the formation of dendrites that grow longer at the anode as the number of cycles increases, eventually passing through the separator to the cathode side, causing internal short circuits. cause. This possibility caused problems similar to those that plagued the lithium metal battery industry in the late 1980s, and eventually ended production of virtually all lithium metal cells in the early 1990s.

These two problems are solved by providing a nanostructured anode between the anode current collector and the porous separator. This nanostructure anode is composed of nanographene platelets (NGP, aggregates of graphene monolayers and multilayers, graphene oxide, graphene fluoride, doped graphene, etc.), carbon nanotubes (single wall or multiwall), carbon nanofibers (gas phase method) It is preferably made of a nanocarbon material having a high specific surface area (preferably more than 100 m ² / g) such as irregular carbon, metal nanowire, conductive nanowire, etc. The nanostructured anode has a specific surface area of more than 100 m ² / g, preferably more than 500 m ² / g, more preferably more than 1000 m ² / g, even more preferably more than 1500 m ² / g, most preferably more than 2000 m ² / g. It is suitable to have. These surfaces are preferably in direct contact with an electrolyte (preferably an organic liquid electrolyte) from which lithium ions are directly taken and lithium ions are released directly.

The placement of the nanostructure anode significantly increases not only the power density (Kw / Kg) of the surface-mediated lithium ion exchange energy storage device, but also the energy density (Wh / Kg). Without wishing to be limited by theory, we believe that this newly provided nanostructured anode plays at least three roles:
(1) During the recharge cycle, the large surface area of this nanostructured anode rapidly deposits a large amount of lithium ions simultaneously at high current density conditions (high charge rate). This can recharge the energy storage device in seconds or fractions of a second.
(2) During the first discharge operation of the newly created surface mediated energy storage device of the present invention, the lithium foil or lithium particles are ionized and released at the anode, move to the cathode side, and are moved by the graphene surface of the cathode It is captured. Upon recharging, these lithium ions return to the anode and deposit uniformly on the large surface of the nanostructured anode, forming an ultrathin coating of lithium. Such a very large surface area of the lithium modified surface releases a large amount of lithium ions simultaneously during the subsequent discharge cycle. This simultaneous release of large amounts of lithium ions was not feasible in a battery equipped with an anode current collector with a specific surface area usually less than 1 m ² / g. The high specific surface area (100 m ² / g or more) of the nanostructured anode allows for rapid charging and discharging and achieves high power density.
(3) The nanostructured anode electronically connected to the current collector provides a uniform electric field in the anode space so that the returned lithium ions can be deposited more uniformly on the surface of the nanomaterial (eg, graphene). Because a large surface area is available for this purpose, only a very small amount of lithium, insufficient for dendritic growth, is deposited on any one spot. These grounds indicate that the surface-controlled energy storage device of the present invention is a safer energy storage device.

The surface-mediated lithium ion exchange battery device is clearly different from the conventional supercapacitor of the following mode.
(1) Conventional or previous supercapacitors do not have a lithium ion source provided at the anode during cell manufacture.
(2) The electrolyte used in these conventional supercapacitors contains almost no lithium or is non-lithium. Even when a lithium salt is used in the electrolyte of the supercapacitor, the solubility of the lithium salt in the solvent is (in the vicinity, not on the electrode material surface as shown in FIG. 3B), the charge inside the electrolyte phase. The upper limit of the amount of lithium ions related to the formation of the electric double layer is substantially set. As a result, the specific capacity and energy density of the resulting supercapacitor is relatively low (eg, generally in the total cell weight, for example, 160 Wh / kg (based on the total cell weight) of the surface mediated cell of the present invention. Based on less than 6 Wh / kg).
(3) Conventional supercapacitors are based on either an electric double layer (EDL) mechanism or a pseudo-capacitance mechanism to store charge. In both mechanisms, a large amount of lithium ions is not exchanged between the two electrodes (even when a lithium salt is used in the electrolyte). For example, in the EDL mechanism, a cation and an anion in the electrolyte are paired to form a charge electric double layer near (but not on) the surface of the electrode active material. Cations are not taken up or stored in or on the electrode active material. On the other hand, in the case of using graphene which is an example of the electrode activator material in the surface mediated cell of the present invention, a lithium atom at a defect site, a graphene edge, a benzene ring center of the graphene surface, or a functional group on the graphene surface Is captured or confined.
(4) In EDL, both cations and anions coexist in both anode and cathode when the supercapacitor is charged. For example, in one of the two electrodes of a symmetric supercapacitor, there is a negative charge on the surface of the activated carbon particles that attracts positively charged species to form a layer of positive charge near these surfaces. Similarly, however, there are nearby negatively charged species attracted by these positive charges to form a layer of negative charges. The opposite electrodes of the supercapacitor are similarly arranged, but the charges are of opposite polarity. This is a well-known concept of Helmholtz's diffuse charge layer in electrochemistry. When the supercapacitor is discharged, the charge on the activated carbon particle surface is used or disappears, resulting in randomization of the negative and positive charge species of the salt within the electrolyte phase (not the activated carbon particle surface). stay. In contrast, when the SMC is in a charged state, most of the lithium ions are attracted and deposited or electroplated on the anode graphene surface, leaving virtually no lithium on the cathode side. After discharge, substantially all of the lithium atoms are taken up by the surface of the cathode active material, with or without a slight retention of lithium inside the electrolyte.
(5) A conventional symmetrical supercapacitor (EDL supercapacitor) using a lithium salt organic electrolyte operates only in the range of 0 to 3 volts. They cannot operate above 3 volts, have no additional charge storage capacity beyond 3 volts, and in fact organic electrolytes generally begin to break down at 2.7 volts. In contrast, the surface mediator cell of the present invention is typically in the range of 1.0 to 4.5 volts, and more typically in the range of 1.5 to 4.5 volts (see, eg, FIG. 9). Operates, but is preferably in the range of 1.5 to 4.0 volts. The range of these two operating voltages is entirely due to the different charge storage mechanisms. Even though it appears that there is an overlap of 1.5-3.0 volts between these two voltage ranges on the paper, the two very different in FIG. 9 because the charge storage mechanism is fundamentally different. As evidenced by cycle voltammetry (CV), this overlap is an artificial, coincidence and not scientifically meaningful.
(6) Conventional EDL supercapacitors typically have an open circuit voltage of 0 to 0.3 volts. In contrast, SMCs are generally greater than 0.6 volts, preferably greater than 0.8 volts, more preferably greater than 1.0 volts (depending on the type and amount of anode active material relative to the cathode, the amount of lithium source). , Some have open circuit voltages in the range of more than 1.2 volts or higher, more than 1.5 volts.
(7) The Lagone plots of FIGS. 10A and 10B accurately show that the surface mediator cell of the present invention is a different energy storage cell class than both supercapacitors and lithium ion batteries.
(8) FIG. 11 shows the cycle performance of several SMCs: cell N (graphene-based), cell AC (activated carbon) and cell M (exfoliated graphite derived from artificial graphite). This result shows that some of the SMCs show a continuous increase in capacity after many charge / discharge cycles (after some minor initial degradation), and also the specificity of SMC that is different from either supercapacitors or lithium ion batteries Indicates.

Charge storage mechanism and energy density considerations Rather than wishing to be limited by theory, the specific capacity of the electrode in a lithium ion exchange surface mediated cell (SMC) is a nanostructured carbon material that can incorporate lithium ions in or on it. Seems to be determined by the number of active sites on the graphene surface. As described above, the nanostructured carbon material includes activated carbon (AC), carbon black (CB), hard carbon, soft carbon, exfoliated graphite (EG), natural graphite or artificial graphite-derived isolated graphene sheet (nanographene platelet or NGP) may be selected. These carbon materials have a common constituent graphene or graphene-like aromatic ring structure. As discussed above, we believe there are four possible lithium storage mechanisms.
Mechanism 1: The geometric center of the benzene ring on the graphene surface is the active site that takes lithium atoms into it.
Mechanism 2: The defect site on the graphene sheet can confine lithium ions.
Mechanism 3: Cations (Li ⁺ ) and anions (derived from lithium salts) in the liquid electrolyte can form an electric double layer of electric charge in the vicinity of the electrode material surface.
Mechanism 4: The functional group on the graphene surface / edge can form a redox pair with lithium ions.

Surface bonding mechanism (mechanism 1): Lithium atoms can form a stable interaction with carbon atoms on the graphene surface when there is no electrolyte for lithium. Li—C bonds in such layers (having no functional groups) will not result in the conversion of carbon orbitals from sp ² to sp ³ . Energy calculations show the possible stability of lithium atom-absorbing graphene layers (having lithium atoms bonded to the benzene ring center of the graphene surface) in the absence of such an electrolyte. Surprisingly, we observed that a lithium-absorbing graphene layer (FIG. 3D) was spontaneously formed in the presence of electrolyte. Lithium ions have a good chemical affinity with other components in the electrolyte (since it is naturally present in the electrolyte), and these components are not “forced deprived” by the graphene surface This was unexpected because the element (eg, solvent) would compete with the graphene surface in an attempt to retain lithium ions in the solvent phase. The bond between the lithium atom and the graphene surface is surprisingly strong.

  Lithium ion confinement at defect sites (Mechanism 2): Active defects such as edges and vacancies (eg, FIG. 3D) in the carbonaceous material can accommodate additional lithium. NGP has a large number of these defects or irregular sites that are inevitably caused by the oxidation-reduction process normally used for graphene production.

Electric double layer (EDL) (mechanism 3): SMC electrolytes generally contain a lithium salt dissolved in a solvent. Charged salts include lithium perchlorate (LiClO ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium borofluoride (LiBF ₄ ), lithium hexafluoroarsenide (LiAsF ₆ ), lithium trifluorometasulfonate (LiCF ₃ SO ₃ ) or the like. In principle, as shown in FIG. 3B, some electric double layers (EDL) are conceptually represented by cations (eg Li ⁺ ) and counter ions (eg PF ₆ ⁻ and BF ₄ ⁻ anions). This EDL that is formed and contributes to the energy storage capacity of the SMC cell is determined by the electrolyte salt concentration in the solvent.

The maximum contribution of mechanism 3 to the overall charge storage capacity to obtain a sufficient amount of electrode surface area is defined by the cation or anion concentration. The EDL mechanism typically contributes less than approximately 10% (more typically less than 5%) of the total lithium ion storage capacity of the SMC described below. We have two separate graphene or other nanostructured electrodes (anode and cathode with different composition), respectively, the anode does not have lithium metal foil / powder that is a lithium source and is lithiated Not several symmetric supercapacitors were prepared and tested. For example, FIG. 9 shows a CV diagram of a graphene supercapacitor and a corresponding SMC. In both cells, the electrolyte is 1M LiPF ₆ / EC + DMC and the scan rate is 25 mV / s. It is interesting to note that this organic electrolyte operates only below 0-2.7 volts in a symmetric supercapacitor configuration and 1.5-4.5 volts in an SMC configuration. This is most surprising because there is no organic electrolyte (based on organic solvents) in supercapacitors that can operate up to 4.0 volts (typically less than 3.5 volts, more typically below 3.0 volts) That is. Organic electrolytes are defined as electrolytes that are not based on water or ionic liquids but contain organic solvents. The capacity showing an overlap voltage range of 1.5 to 2.7 volts covers less than 5% of the total capacity of the SMC. In fact, the operation of SMC is mainly via surface uptake, not within the electric double layer formation, even within the voltage range of 1.5-2.7 volts.

  Formation of redox couple (mechanism 4): The surface redox reaction is performed by a functional group such as a carbonyl group (> C═O) or a carboxyl group (—COOH) as shown in FIG. If) and lithium ions. The presence of functional groups such as -COOH and> C = O in chemically prepared graphene oxide is well documented. The formation of these functional groups is a natural result of the oxidation reaction of graphite with sulfuric acid and strong oxidants (eg mass production and potassium permanganate commonly used for the preparation of graphene oxide). Unseparated graphite worms (exfoliated graphite) and separated graphene sheets (NGP) have surface or end-forming functional groups. In one embodiment, SMC in this application is primarily based on mechanisms 1 and 2.

  In general, the electric double layer mechanism contributes less than 10% (mainly less than 5%) of the SMC's charge storage capacity. When either the anode or the cathode is a multilayer graphene platelet, lithium intercalates into the bulk of the active material when the SMC operating voltage is below 1.5 volts. Even in this case, no more than 20% of the lithium is stored in the bulk of the anode active material when the device is in the charged state and no more than 20% of the lithium is stored in the bulk of the cathode active material when the device is in the discharged state. The Generally, no more than 10% of the lithium is stored in the bulk of the anode active material when the device is in a charged state, and no more than 10% of the lithium is stored in the bulk of the cathode active material when the device is in a discharged state. The

  The nanostructured material used for the anode or cathode of the present invention preferably contains nanographene platelets (NGP), carbon nanotubes (CNT) or irregular carbon. These nanostructured carbon materials are used as support substrates for other organic or polymerizable functional materials that have useful functional groups (eg, carbonyl groups) but are not conductive. CNT is a well-known material in the nanomaterials industry and will not be discussed further here. Below, it describes about NGP and nanostructure irregular carbon.

Nano graphene platelet (NGP)
The applicant's research group is actively developing applications of single-layer graphene (Patent Document 5), including the use of graphene for supercapacitors (Patent Document 3) and the use of graphene for lithium ion batteries (Patent Document 4) .

  Single layer graphene or graphene face (a layer of carbon atoms forming a hexagonal or honeycomb structure) is common to a series of graphite materials including natural graphite, artificial graphite, soft carbon, hard carbon, coke, activated carbon, carbon black, etc. It is a structural unit. In these graphite materials, multilayer graphene sheets are generally stacked along the graphene thickness direction to form regular domains or crystals of graphene surfaces. Multi-layered crystals of domains combine with irregular or amorphous carbon species. In the present application, we can extract or isolate these crystals or domains to obtain multilayer graphene platelets from irregular carbon species. In some cases, we exfoliate and separate these multilayer graphene platelets within an isolated single layer graphene sheet. In other cases (for example in activated carbon, hard carbon and soft carbon) we chemically remove some irregular carbon species to widen the gate and enclose the liquid electrolyte inside (exposing the graphene surface to the electrolyte). Removed.

  In the present application, “nanographene platelet (NGP)” or “graphene material” as a whole means single-layer and multilayer embodiments such as graphene, graphene oxide, graphene fluoride, graphene hydroxide, graphene nitride, and doped graphene.

  Due to the definition of NGP geometry, NGP is described as having length (maximum dimension), width (second dimension) and thickness. The thickness is the minimum dimension, and in the present application is 10 nm or less (preferably 5 nm or less). NGP may be single layer graphene. If the platelet is approximately circular, the length and width are called the diameter. In the NGP defined here, the length and width are not limited, but are preferably smaller than 10 μm, more preferably smaller than 1 μm. We can produce NGP with a length less than 100 nm or greater than 10 μm. NGP is pure graphene (with an oxygen content of substantially 0%, generally less than 2%) or graphene oxide (with an oxygen content of generally up to 10 to about 45% by weight). The graphene oxide is thermally or chemically reduced to reduced graphene oxide (generally having an oxygen content of 1 to 20% by weight, more preferably less than 5% by weight). In the use of the anode and / or cathode of the lithium superbattery and functional material based surface control cell disclosed in our prior application, the oxygen content is preferably in the range of 5-30% by weight, More preferably, it is in the range of% by weight. However, in the present application, SMC electrodes generally have an oxygen content of less than 5% by weight (and therefore substantially no functional groups), often less than 2%. The specific surface area that can contact the liquid electrolyte is the single most important parameter that defines the energy density and power density of the SMC.

  Despite the exceptionally high specific surface area of individual graphene sheets, planar graphene sheets prepared by conventional routes are more likely to overlap or overlap again, thereby allowing the specific surface area accessible by the electrolyte Is dramatically reduced. FIG. 5A shows graphene called a curved graphene platelet or sheet. Curved NGP can form a mesoporous structure with a desired pore size range (eg, just over 2 nm) when overlapping to form an electrode. This size range appears to be conductive that can be contacted by commonly used lithium-containing electrolytes.

The curved NGP is manufactured by the following process.
(A) Dispersing laminated graphite material (eg natural graphite powder) in a mixture of intercurrent and oxidant (eg concentrated sulfuric acid and nitric acid respectively) to obtain graphite intercalation compound (GIC) or graphite oxide (GO) Or the process of immersing.
(B) To obtain exfoliated graphite or graphite worms (if the intercalation / oxidation process is carried out for a sufficiently long duration, eg more than 24 hours, oxidized NGP with a thickness of less than 100 nm is formed at this stage) A step of exposing the obtained GIC or GO to a heat shock for a short time (generally 15 to 60 seconds), preferably in a temperature range of 600 to 1100 ° C.
(C) A liquid medium optionally containing a functionalizing agent to form a suspension (eg sulfuric acid, nitric acid, hydrogen peroxide, or preferably carboxylic acid, formic acid, etc., which is the source of —COOH groups) ) To disperse. Diffusion, mechanical shearing, sonication and / or temperature are used to decompose the graphite worm. In order to obtain a graphene liquid suspension, the separated / isolated NGP is formed and / or the desired functional groups are attached to the oxidized NGP to form the functionalized NGP.
(D) aerosolizing the graphene suspension into droplets optionally containing chemically functionalized single or multiple NGPs while simultaneously removing liquid to recover curved NGP; When the aerosolization step is not provided, the obtained graphene platelet tends to be planar.

  Steps (a) to (b) are the most commonly used steps in this field for obtaining exfoliated graphite (FIG. 5B) and graphene oxide platelets. Oxidized NGP or GO platelets are chemically reduced using hydrazine as a reducing agent to restore conductivity before, during or after chemical functionalization.

In one embodiment, environmentally friendly carboxylic acids are particularly desirable functionalizing agents for imparting carbonyl or carboxyl groups to NGP. Carboxylic acids include aromatic carboxylic acids, aliphatic or cycloaliphatic carboxylic acids, linear or side chain carboxylic acids, saturated and unsaturated monocarboxylic acids, dicarboxylic acids and polycarboxylic acids having 1 to 10 carbon atoms, and alkalis thereof. It can be selected from the group consisting of esters and combinations thereof. Preferably, the carboxylic acid is formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, the formula _{H (CH} 2) containing hexanoic acid n saturated aliphatic carboxylic acid COOH (n = 0 to 5), an anhydride thereof, These reactive carboxylic acid derivatives are selected from the group consisting of combinations thereof. The most preferred carboxylic acids are formic acid and acetic acid.

NGP may perform the following processing separately or in combination before or after the functionalization operation.
(I) Chemical functionalization with different functional groups. Other useful surface functional groups include quinone, hydroquinone, quaternized aromatic amines or mercaptans.
(Ii) Coating or grafting with a polymer containing a desired functional group (for example, a carbonyl group).
(Iii) Activation treatment (similar to activation of carbon black material) to form additional surfaces and impart functional chemical groups to these surfaces. Activation treatment, CO ₂ physical activation, KOH chemical activation, or is achieved through exposure nitrate, the fluorine or ammonia plasma.

  The above process produces graphene oxide platelets or oxidized NGP. The heavy oxidation steps involved in these processes essentially incorporate oxygen-containing groups on both the NGP end and basal surfaces (top and bottom). This is both good and bad. On the one hand, we want to create as many functional groups as possible to maximize lithium uptake performance. On the other hand, however, functional groups on the base or graphene surface damage the surface and significantly reduce the overall conductivity of NGP. The formation of functional groups in this manner without the step (c) is not a well controlled step.

  A further method of imparting functional groups to NGP in a controlled manner involves the production of pure NGP without performing it through a conventional chemical intercalation / oxidation process. Non-oxidized graphene produced (essentially with more chemically active end surfaces) performs controlled oxidation or controlled functionalization. The functional group is first attached to the end surface and essentially depletes the active site at the end surface before a significant amount of functional group begins to attach to the basal plane.

  In 2007, we reported a direct sonication method for the direct production of pure nanographene from graphite particles dispersed in a surfactant-water suspension (Patent Document 6). This method involves the dispersion of natural graphite particles in a low surface tension liquid such as acetone or hexane. The obtained suspension is subjected to direct ultrasonic treatment for producing graphene for 10 to 120 minutes at a rate of peeling 20,000 graphene sheets per second per particle. Graphite is not intercalated or oxidized, so no subsequent chemical reduction is required. This method is fast, environmentally friendly and easily scaled up to achieve mass production of pure nanographene materials. The same method is later studied by others and is called normal “liquid phase manufacturing”. When pure graphene is produced, the material is exposed to an oxidation or functionalization process, for example using a gas phase or a liquid acid or acid mixture. Pure NGP is immersed in the carboxylic acid at the desired temperature and for the desired time to obtain NGP functionalized at the desired level.

Specifically, the oxidation treatment is preferably a step of applying a pure NGP material to an oxidant selected from ozone, sulfonic acid (SO ₃ ) vapor, oxygen-containing gas, hydrogen peroxide vapor, nitric acid vapor, and combinations thereof. including. Preferably, the treatment includes applying pure NGP material to the oxidant in a hydrogen-containing environment. Oxidation is performed by immersing NGP in a liquid acid and / or oxidant environment, but such a process requires a subsequent water washing and purification step (such a washing process is a conventional sulfuric acid-intermediate). Not as tedious as required for calation graphite). Accordingly, gas treatment that does not require post-cleaning treatment is preferred.

  Conductive functionalized NGP is produced with an oxygen content of 25 wt% or less, preferably 5-25 wt%. Perhaps the majority of the functional groups are located on the end surface of NGP because of the significant reduction in electrical conductivity. When the total oxygen content is greater than 25%, functional groups begin to appear on the graphene surface and interrupt the electron conduction path. The oxygen content was measured using chemical elemental analysis and X-ray photoelectron microscopy (XPS).

  Partially oxidized NGP is further functionalized by performing an additional step of contacting the partially oxidized NGP with a reactant to add functional groups to the surface or edges of the nanographene platelets. Functional groups include alkyl or allyl silane, alkyl or aralkyl groups, hydroxyl groups, amine groups, fluorocarbons, and combinations thereof.

NGP has a reactive graphene surface (RGS) or a reactive graphene edge (REG) after partial oxidation treatment. These are described as performing the following reactions.
(A) RGS / RGE + CH ₂ = CHCOOX (at 1000 ° C.) → graphene-R′COH (X = —OH, —Cl or —NH ₂ ), for example, RGS / RGE + CH ₂ = CHCOOH → G—R′CO—OH ( G = graphene)
(B) RGS / RGE + maleic anhydride → GR ′ (COOH) _{2
(C) RGS / RGE + CH} 2 = CH-CH 2 X → G-R'CH 2 X (X = -OH, - halogen or _-NH 2)
(D) RGS / RGE + H ₂ O → G═O (quinoid type)
(E) RGS / RGE + CH ₂ ═CHCHO → GR′CHO (aldehyde system)

In the above reaction, R ′ is a hydrocarbon radical (alkyl, cycloalkyl, etc.). The partial oxidation of pure NGP is induced by the attachment of several functional groups including carboxylic acids and hydroxyl groups on the surface or edge of the graphene surface. Many derivatives are prepared from carboxylic acids. For example, alcohols or amines readily couple with acids to provide stable esters or amides. Any reaction of attaching a carbonyl group (> C═O) or an amine group (—NH ₂ ) to the graphene edge or basal surface is used in the practice of the invention.

Nanostructured Irregular Carbon Irregular carbon materials are a series of carbonaceous materials such as soft carbon, hard carbon, polymerizable carbon (or carbonized resin), mesophase carbon, coke, carbonized pitch, carbon black, activated carbon, and partially graphitized carbon. Selected from materials. As schematically shown in FIGS. 3A and 3B, the irregular carbon material generally consists of two phases. The first phase is a small graphite crystal or a small stack of graphite faces (generally up to 10 graphite faces or 10 aromatic ring structures that are overlapped to form small ordered domains) and the second phase is amorphous carbon. Yes, the first phase is dispersed in or bound by the second phase. The second phase consists mainly of small molecules, small aromatic rings, defects, and amorphous carbon. Any desired functional groups (eg, —COOH and NH ₂ groups in FIG. 3B) are attached to the end or flat surface of the aromatic ring structure. In general, irregular carbon exists in the form of ultra fine powders (eg, carbon black) having high porosity (eg, activated carbon) or nanoscale features (and hence high specific surface area).

  Soft carbon is a carbonaceous material composed of small graphite crystals, and the direction of the stack of these graphite crystals or graphene sheets is further bonded to adjacent graphene sheets using high temperature heat treatment (graphitization) or these graphite crystals or graphene stacks This is useful for further growth (FIG. 4A). Therefore, it can be said that soft carbon can be graphitized.

  Hard carbon (FIG. 4B) is a carbonaceous material composed of small graphite crystals, and the stacks of these graphite crystals or graphene sheets are not oriented in a preferred direction (eg, substantially perpendicular to each other) and therefore adjacent graphene sheets Or further growth of these graphite crystals or graphene stacks (useless, ie cannot be graphitized).

  As schematically shown in FIG. 4C, carbon black (CB), acetylene black (AB) and activated carbon (AC) are generally composed of domains of aromatic rings or small graphene sheets, and aromatic rings Alternatively, adjacent domain graphene sheets are somehow connected through several chemical bonds in an irregular phase (matrix). These carbon materials are usually obtained from the thermal decomposition (heat treatment, thermal decomposition or firing) of hydrocarbon gas or solution or natural products (wood, coconut shell, etc.).

  The preparation of polymerizable carbons by simple pyrolysis of polymer or petroleum / coal tar pitch materials has been known for about 30 years. When polymers such as polyacrylonitrile (PAN), rayon, cellulose and phenol formaldehyde are heated at about 300 ° C. in an inert atmosphere, they gradually lose most of their non-carbon content. The resulting structure is commonly referred to as polymerizable carbon. Depending on the heat treatment temperature (HTT) and time, the polymerizable carbon is insulated, semiconducted or made conductive with an electrical conductivity range covering about 12 orders of magnitude. This wide range of conductivity values is further expanded by doping the electron donor or acceptor with polymerizable carbon. These unique features view polymerizable carbon as a new and easily processable electron-accepting material that can be easily tuned in structure and physical properties.

  Polymerizable carbon is assumed to be essentially an amorphous structure or has a stack of many graphite crystals or graphene faces dispersed in an amorphous carbon matrix. Depending on the HTT used, various proportions and sizes of graphite crystals and defects are dispersed in the amorphous matrix. Various amounts of two-dimensional compressed aromatic rings or hexagons (graphene surface precursors) are found inside the microstructure of heat treated polymers such as PAN fibers. It is considered that a small amount of graphene sheet that can be sensed exists in PAN-based polymerizable carbon treated at 300 to 1000 ° C. These species are compressed into wide aromatic ring structures (large graphene sheets) and thick planes (stacked graphene sheets) with high HTT (eg above 1500 ° C.) or long heat treatment times. A stack of these graphene platelets or graphene sheets (base plane) is dispersed in an amorphous carbon matrix. Such a two-phase structure is characteristic of some irregular carbon materials.

  There are several classes of precursor materials in the irregular carbon material of the present application. For example, the first class includes fiber-shaped semicrystalline PAN. Compared to phenolic resins, pyrolytic PAN fibers have a higher tendency to grow small crystals dispersed in an irregular carbon matrix. The second class represented by phenol formaldehyde is more isotropic, essentially amorphous and highly crosslinked polymers. The third class includes petroleum and coal tar pitch materials in bulk or fiber shape. Precursor material composition, heat treatment temperature (HTT) and heat treatment time (Htt) control length, width, thickness (number of graphene faces in the graphite crystal) and chemical composition of the resulting irregular carbon material 3 There are two parameters.

  In this study, in order to obtain polymerizable carbons having various nanocrystalline graphite structures (graphite crystals), the PAN fiber was oxidized at 200 to 350 ° C. under tension, followed by 350 to 1500 ° C. Partial or complete carbonization was performed. In order to partially graphitize the material and maintain the desired amount of amorphous carbon (> 10%), selected samples of these polymerizable carbons were further heat treated at a temperature range of 1500-2000 ° C. The same heat treatment was performed on the phenol formaldehyde resin and petroleum and coal tar pitch materials in the temperature range of 500-1500 ° C. Irregular carbon material obtained from PAN fiber or phenolic resin can be activated using processes commonly used to produce activated carbon (eg treated for 1-5 hours in KOH dissolved at 900 ° C.). Preferably it is done. This activation treatment forms an irregular carbon mesoporous that allows the liquid electrolyte to reach the end or surface of the aromatic ring constituting the SMC device. Such an apparatus easily arranges lithium ions in a solution on the surface of graphene without performing solid state diffusion.

  Certain grades of petroleum pitch or coal tar pitch may be heat treated (generally 250-500 ° C.) to obtain an optically anisotropic structure of liquid crystal type, usually called mesophase. This mesophase material can be extracted from the liquid components of the mixture to produce mesophase particles or spheres. Optionally, these mesophase particles or spheres may be further subjected to a graphitization heat treatment.

Physical or chemical activation is used to obtain all kinds of irregular carbons (eg soft carbon, hard carbon, polymerizable carbon or carbonized resin, mesophase carbon, coke, carbonized pitch, carbon to obtain activated irregular carbon. Black, activated carbon, partially graphitized carbon). For example, the activation process can be achieved through oxidation, CO ₂ physical activation, KOH or NaOH chemical activation, exposure to nitric acid, fluorine or ammonia plasma (forms electrolyte accessible pores rather than functionalization). For).

The functionalization process of nanostructured irregular carbon is similar to the process used for NGP and therefore will not be repeated here. In particular, any reaction in which a carbonyl group (> C═O) or an amine group (—NH ₂ ) is attached to the graphene end portion or basal plane surface of an irregular carbon material can be used in the present invention.

Lithium Reactive Functional Group-Containing Organic and Polymerizable Functional Materials Many organic or polymerizable functional materials may contain the following functional groups that react rapidly and reversibly with lithium ions in a liquid or gel electrolyte. Examples include poly (2,5-hydroxy-1,4-benzoquinone-3,6-methylene), Li _x C ₆ O ₆ (x = 1 to 3), Li ₂ (C ₆ H ₂ O ₄ ), _{Li 2 C 8 H 4 O 4} (Li _{terephthalate), Li 2 C 6 H 4} O 4 (Li trans - trans - muconate), 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) sulfide Polymer, PTCDA, 1,4,5,8, -naphthalene-tetracarboxylic dianhydride (NTCDA), benzene-1,2,4,5-tetracarboxylic dianhydride, 1,4,5,8- Tetraanhydroanthraquinone, tetraanhydro-p-benzoquinone and combinations thereof are included. These functional molecules, polymers or salts usually have a relatively low electrical conductivity which is not useful as an electrode material by itself. One exception is sulfur cross-linked PTCDA (PTCDA sulfide polymer).

  Some of these non-conductive functional materials are suitably combined with nanostructured materials such as NGP, CNT, disordered carbon, nanowires and nanofibers (eg, chemical bonding or attachment). For example, the aromatic ring of the constituent elements of graphene and irregular carbon (soft carbon, hard carbon, activated carbon, carbon black, etc.) is a functional group on the functional material (for example, a hydroxyl group on tetraanhydro-p-benzoquinone). It has a functional group that can react on its end or surface. These organic or polymerizable functional materials may also be simply supported on the surface of a nanostructured material (eg, a graphite or nanowire surface). Nanostructured materials (eg, graphene and disordered carbon) may be functionalized to provide not only support for organic or polymerizable materials (giving electrical conductivity), but also functional groups that can react with lithium. .

  In short, the cathode active material and / or anode active material of the SMC of the present invention is (a) soft carbon, hard carbon, polymerizable carbon or carbonized resin, mesofuse carbon, coke, carbonized pitch, carbon black, activated carbon or partial graphite. Porous irregular carbon material selected from carbonized carbon, (b) graphene monolayer sheet or multilayer platelet, graphene oxide, graphene fluoride, graphene hydroxide, graphene nitride, boron-doped graphene, nitrogen-topped graphene, functionalized Graphene material selected from graphene or reduced graphene oxide, (c) exfoliated graphite, (d) mesoporous carbon, (e) carbon nanotubes selected from single-walled carbon nanotubes or multi-walled carbon nanotubes, (f) carbon Nanofibers, metal nanowires, metal oxide nanowires, or fibers, or, conductive polymers nanofibers may be selected from these combinations, (g).

  The following examples are useful for illustrating the preferred embodiments of the present invention, but should not be construed as limiting the spirit of the invention.

<Example 1>
Functionalized and non-functionalized soft carbon (a type of irregular carbon), soft carbon super battery and surface intervening cell

  Non-functionalized and functionalized soft carbon materials were prepared from liquid crystalline aromatic resins. This resin was pulverized with mortar and calcined at 900 ° C. for 2 hours in a nitrogen atmosphere to prepare graphitized carbon or soft carbon. The resulting soft carbon was mixed with a small amount of KOH tablet (4 times weight) in an aluminum crucible. Subsequently, the KOH-containing soft carbon was heated at 750 ° C. for 2 hours in a nitrogen atmosphere. After cooling, the alkali-rich residual carbon was washed with warm water until the waste liquid reached pH 7. The resulting material is activated non-functionalized soft carbon.

Apart from the above, as an oxidation treatment, a part of the activated soft carbon was immersed in a 90% H ₂ O ₂ -10% H ₂ O solution at 45 ° C. for 2 hours. Then, the partially oxidized soft carbon obtained was immersed in formic acid at room temperature for functionalization. The resulting functionalized soft carbon was then dried by heating in a vacuum oven at 60 ° C. for 24 hours.

A coin cell using a functionalized soft carbon as a cathode and a functionalized soft carbon as a nanostructure anode (and a lithium foil slice as a lithium source mounted between a current collector and a separator layer, Sample-1) was prepared. Tested. For comparison, a non-functionalized corresponding cell (Sample-1b) was also prepared and tested. A single microporous membrane (Celgard 2500) was used as a separator in all cells. The current collector of each of the two electrodes was a single carbon-coated aluminum foil. The composition of the electrode was 85 wt% soft carbon (and 5 wt% Super-P coated on aluminum foil and 10 wt% PTFE binder). The electrolyte solution was obtained by dissolving LiPF ₆ in 1M in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 3: 7. In order to reduce the background current, the separator was wetted with a minimum amount of electrolyte. Cyclic voltammetry and constant current measurements of the lithium cell were performed at room temperature (in some cases at a low temperature of −40 ° C. and a high temperature of 60 ° C.) using an Arbin 32-channel supercapacitor-battery tester.

  As a reference sample (Sample-1-CA), a similar coin cell with a single lithium foil on the anode but no nanostructured carbon layer was made and tested. This is a conventional lithium super battery. In addition, a symmetric supercapacitor (Sample-1-CB) comprising both electrodes made of a functionalized soft carbon material and not including an additional lithium source that can be used in a liquid electrolyte was also prepared and evaluated. This data was compared with data from Lee et al.'S conventional symmetrical supercapacitor (f-LBL-CNT / f-LBL-CNT).

Super battery (sample-1CA) containing functionalized soft carbon bulk material (thickness less than 200 μm) as cathode active material, corresponding surface control battery cell (sample-1) and non-functionalized surface mediating cell (sample-1b) This constant current study yields important data as summarized in the Lagone plot and cycle stability data of FIG. 6A (FIG. 6B). These plots give the following results:
(A) Functionalized and non-functionalized surface-controlled lithium ion exchange battery devices exhibit significantly higher energy and power densities, especially than corresponding super batteries with relatively high current density (high power density data points in the plot) . This is due to the presence of the nanostructured anode (in addition to the nanostructured cathode), during the recharge and discharge cycles, a high proportion of lithium ions are each deposited on and released from a wide surface area of the anode. Which indicates that. A conventional superbattery with a current collector having a limited specific surface area as an anode provides a sufficient amount of surface area for use by lithium ions to deposit or release from the surface area at the same time I can't. The entire charge and discharge process is limited in surface.
(B) Both-surface-controlled lithium ion exchange battery devices include a corresponding symmetric supercapacitor (sample-1-CB) that does not have a lithium foil as a lithium source, and Lee et al. Functionalized LBL-CNT anode and functionalized LBL-CNT. The energy density and output density are significantly higher than those of conventional supercapacitors made of a cathode. In fact, two symmetrical supercapacitors (without a lithium source) based on either irregular carbon or LBL-CNT had dramatically different thicknesses of the two electrodes (irregular carbon electrode thickness). Is more than 100 μm and the thickness of the LBL-CNT electrode is less than 3.0 μm). This is the manifestation of the local surface absorption or electric double layer mechanism associated with conventional supercapacitors that do not require long-range movement of change (especially not requiring lithium ion exchange between the anode and cathode). Let's go. The amount of lithium ions and counter ions (anions) is limited by the solubility of the lithium salt in the solvent. The amount of lithium incorporated and stored on the active material surface of the electrode is dramatically higher than this solubility limit.
(C) As described above, the output density of known supercapacitors is generally 5,000 to 10,000 W / KG, while that of a lithium ion battery is 100 to 500 W / kg. This means that the surface mediated lithium ion exchange cell has an energy density comparable to that of modern batteries that is 5 to 16 times higher than the energy density of conventional supercapacitors. SMC also exhibits a power density (or charge-discharge ratio) that is significantly higher than the power density of conventional electrochemical supercapacitors.
(D) SMCs based on non-functionalized surfaces perform significantly better than corresponding functionalized surface control cells with respect to energy density and power density.
(E) In particular, non-functionalized surface-mediated cells exhibit better cycle stability compared to functionalized material-based cells. As shown in FIG. 6B, the non-functionalized surface cell maintains a high energy density even after 2500 charge / discharge cycles. However, functionalized surface control cells are subject to faster degradation due to repeated charging / discharging.
(F) The calculation from the obtained data shows that the number of discharges of the conventional super battery is 19 seconds at a current density of 10 A / g. In contrast, the number of discharges of the corresponding SMC is less than 5 seconds at the same current density.
Sample-1 and Sample-1-CA cells have selected functional groups on the surface / end of the aromatic ring on the cathode side (Sample-1-CA) and on both the cathode and anode (Sample-1). Executes a redox reaction of lithium ions. These functional groups attached to both the end of the aromatic ring (small graphene sheet) and the plate surface react rapidly and reversibly with lithium. In many cases, SMCs based on non-functionalized surfaces perform better. The surface-mediated lithium ion exchange battery of the present invention is an innovative new energy storage device that is fundamentally different from supercapacitors and lithium ion batteries. Neither energy density nor power density approximates that of conventional devices.

<Example 2>
MCGP sulfuric acid intercalation and stripping NGP

MCMB2528 microbeads (manufactured by Osaka Gas Chemical Co., Ltd., Japan) have a density of about 2.24 g / cm ³ , a median diameter of about 22.5 microns and a face-to-face distance of about 0.336 nm. MCMB2528 (10 g) was intercalated in acid solution (4: 1: 0.05 sulfuric acid, nitric acid and potassium permanganate) for 24 hours. After completion of the reaction, the mixture was poured into ion exchange water and filtered. In order to remove most of the sulfate ions, the intercalated MCMB was washed repeatedly in a 5% solution of HCL. The sample was then washed with ion exchange water until the pH of the filtrate was neutral. The slurry was dried and stored in a vacuum dryer at 60 ° C. for 24 hours. In order to obtain exfoliated graphite, a dry powder sample was placed in a quartz tube and inserted into a horizontal heating tube furnace preset at a desired temperature of 600 ° C. for 30 seconds. Furthermore, in order to obtain functionalized graphene (f-NGP), the exfoliated MCMB sample was functionalized in formic acid for 30 minutes in an ultrasonic bath at 25 ° C. Non-functionalized NGP was also obtained by sonication of exfoliated MCMB in water without functionalizing reagent.

  NGP was used as the cathode and anode material in the functionalized or non-functionalized surface control battery. Lithium foil was added between the anode and the separator. As a reference super battery, the anode is a lithium foil (not including nanostructured NGP), and the cathode is f-NGP. A lagone plot of these three types of cells is shown in FIG. The energy density and power density of the NGP-based surface-mediated lithium ion exchange battery device is higher than that of the corresponding super battery, especially at relatively high current densities (high power density data points in the plot). This shows the superior performance of SMC on the super battery. Non-functionalized surface mediator cells perform better than functionalized surface control cells in terms of energy density and power density. Quite significantly and surprisingly, when compared to functionalized surface mediator cells, non-functionalized surface mediator cells exhibit good long-term stability with repeated charging / discharging (FIG. 8).

<Example 3>
Organic 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), PTCDA sulfide polymer and nanostructured NGP supported PTCDA

  Enolation is an important reaction of carbon double bonds that are stabilized by a conjugated structure. Enolation allows reversible uptake or release of lithium ions at the oxygen atom position when the carbonyl group is reduced or oxidized, which is used as a novel organic energy storage system in lithium ion batteries. It is shown that. In the reduction step of PTCDA, each carbonyl group forms a lithium enolate, receives one electron, takes in one lithium ion, and releases a lithium ion in the reversible oxidation step.

  Three types of electrodes were prepared for use as the anode and / or cathode of a surface controlled lithium ion exchange battery device. The first type was a simple mixture of PTCDA and carbon black (approximately 20% by weight) bound by PVDF (Sample 3-A).

  The second type (Sample 4-B) was a similar mixture of PTCDA sulfide polymer and carbon black as a conductive filler. A PTCDA sulfide polymer was synthesized by using PTCDA (Bright Red) well mixed by grinding at a mass ratio of 1: 1 and sublimation sulfur as the starting material. The mixture was reacted at 500 ° C. under a flowing argon atmosphere for 3 hours to obtain a black-red powder of PTCDA sulfide polymer. This synthetic route was originally proposed by XY Han et al.

<Example 4>
SMC based on natural graphite, carbon fiber and artificial graphite derived graphene material (NGP) and SMC based on carbon black (CB) and treated CB

  Improved Hummer's method comprising subjecting the starting graphite material to a mixture of sulfuric acid, sodium nitrate and potassium permanganate in a ratio of 4: 1: 0.1 for 72 hours to produce oxidized NGP or graphene oxide (GO). Prepared. The resulting GO was then thoroughly washed with water to obtain a GO suspension resulting from two different material preparation routes. One route involves sonicating the GO suspension to obtain an isolated graphene oxide sheet (Cell-N) suspended in water. Another route involves spray drying the GO suspension to obtain a graphite intercalation compound (GIC) or GO powder. Next, the GIC or GO powder was thermally exfoliated at 1050 ° C. for 45 seconds to obtain exfoliated graphite or graphite worm (cell G). The exfoliated graphite worm derived from artificial graphite and carbon fiber was subjected to ultrasonic treatment to separate or isolate the graphene oxide sheets (cell M and cell C, respectively). Carbon black (CB) was subjected to the same chemical treatment as Hummer's method, the nanogate was expanded, and an electrolyte was introduced inside (cell t-CB).

Each electrode consisting of 85% graphene, 5% Supre-P (AB-based conductive additive) and 10% PTFE was covered with an aluminum foil. The thickness of the electrodes was typically about 150-200 μm, but to evaluate the effect of electrode size on the power and energy density of the resulting supercapacitor-battery cell, thicknesses of approximately 80, 100, 150 μm were used. An additional sample with was prepared. For comparison, an electrode having a thickness of 20 μm was also produced. Prior to use, the electrode was dried in a vacuum dryer at 120 ° C. for 12 hours. The cathode was lithium metal supported on a layer of graphene sheets. Coin size cells were assembled in a glove box using 1M LiPF ₆ / EC + DMC as electrolyte.

<Example 5>
Functionalized and non-functionalized activated carbon

  Activated carbon (AC from Ashbury Carbon) was treated with acid solution (4: 1: 0.05 sulfuric acid, nitric acid and potassium permanganate) for 24 hours. After completion of the reaction, the mixture was poured into ion exchange water and filtered. To remove most of the sulfate ions, the treated AC was washed repeatedly in a 5% solution of HCL. The sample was then washed with ion exchange water until the pH of the filtrate was neutral. The slurry was functionalized in formic acid for 30 minutes in an ultrasonic bath at 25 ° C. Subsequently, in order to obtain a thin layer of chemically functionalized activated carbon (f-CA) having a thickness of typically 20-150 μm coated on the surface of the aluminized carbon layer as the current collector, dip coating Was used. Such an electrode was used as the anode, and the same type of material with a lithium foil provided between the porous separator and one electrode as the lithium source was used as the cathode. A corresponding SMC cell without functionalization was also prepared and tested.

  Capacitors were measured by a constant current test using Arbin SCTS electrochemical test equipment. To reveal the chemical composition and microstructure of NGP and exfoliated graphite samples, cycle voltammetry (CV) was processed on an electrochemical workstation from CHI 660 Instruments. Scanning electron microscope (SEM, Hitachi S-4800), transmission electron microscope (TEM, Hitachi H-7600), FTIR (Perkin Elmer GX FTIR), Raman spectrometer (Renishaw Via) Reflex Micro-Raman) and atomic force microscope were used.

The NGP mediated electrode has a specific capacity of 127 mAh / g at a current density of 0.1 A / g, and is 17 A higher than a typical 5 Wh / kg _{cell of} a commercially available AC-based symmetric supercapacitor. A cell (for example, cell M) is supplied at a current density of 85 Wh / kg _cell (FIG. 8C).

Another graphene surface mediator cell (cell N, FIG. 8D) shows a high energy density of 160 Wh / kg _cell corresponding to that of a lithium ion battery. The energy density of the cell N maintains a value exceeding 51.2 Wh / kg _cell even at a current density of 10 A / g, and realizes an output density of 4.55 kW / kg _cell . The power density of commercially available AC-based symmetric supercapacitors is generally in the range of 1 to 10 kW / kg _{cell with} an energy density of 5 Wh / kg _cell . This shows that the surface mediator achieves an energy density of more than 10 times compared to a conventional supercapacitor with the same power density.

The power density is 25.6 kW / kg _cell at 50 A / g for an energy density of 24 Wh / kg _cell . Power density is increased at 200A / g to 93.7kW _{/ kg cell} relative energy density of 12Wh _{/ kg cell} (Fig. 8 (D)). This power density is an order of magnitude higher than that of a conventional supercapacitor, which is famous for its high power density, and 2 to 3 than that of a conventional lithium ion battery (generally 0.1 to 1.0 kW / kg _cell ). An order of magnitude higher. These data clearly show that surfaceable cells are a class of energy storage cells that are quite different from conventional supercapacitors and lithium ion batteries.

FIG. 8B includes a comparison of CV data showing that carbon fiber-derived graphene has slightly better performance than graphite-derived graphene, which is an electrode active material. This may be the result of a more curved or creased shape of fiber-derived graphene that avoids full face-to-face restacking of the graphene sheets during electrode preparation. The energy density and power density of the exfoliated graphite-based cell (cell G), which is low relative to well-separated NGP-based cells (cells M and C), is the typical 600-900 m of almost isolated single layer graphene sheets ^This may be due to the low specific surface area of EG (generally 200-300 m ² / g based on BET measurements) relative to ² / g.

FIG. 8D shows the energy density and power density of carbon black (CB) by performing an activation / functionalization treatment on CB including a step of exposing to a mixture of sulfuric acid, sodium nitrate and potassium permanganate for 24 hours. It shows that the value increases sufficiently. BET surface area is increased to approximately ^{60m 2} / ^g~300m 2 / g, the capacity it was found that the increase in 8.47mAh / g~46.63mAh / g. A cell with a treated carbon black electrode exhibits output and energy density equivalent to that of an activated carbon electrode.

  FIG. 10 shows a lagone plot of graphene surface capable lithium ion exchange cells with different electrode thicknesses. The energy density and power density values were calculated based solely on the total cell weight in FIG. 10 (A) and the cathode weight in FIG. 10 (B). These data indicate that electrode thickness plays an important role in defining the energy density and power density of SMC. In particular, these data show that SMCs with thick electrodes are ultra-thin used in CNT-based super batteries without using expensive and slow processes (lay-by-layer, LBL proposed by Lee et al.). It clearly shows that it works very well for making electrodes. FIG. 10 also clearly shows that the surface mediator cell is a different energy storage cell class than the supercapacitor and lithium ion battery.

  FIG. 12 shows that the specific surface area of the electrode is one of the most important parameters in defining the lithium storage capacity. The data point with the highest specific capacity in this plot is obtained from chemically reduced graphene oxide. Chemical analysis data indicates that this heavy reduced graphene material has an oxygen content of less than 2.0%, suggesting that it is essentially free of functional groups. Heavy graphene oxide by chemical or thermal reduction is known to have significant surface defect sites. The four data points (denoted by x) are the original graphene electrodes obtained from direct sonication of the graphene material pure graphite (> 99.9%). These data points indicate that a pure graphene surface (having a benzene ring center and no surface defects or functional groups) evenly takes lithium ions from the electrolyte and stores a corresponding amount of lithium per surface area unit It is shown that.

  The long-term stability of these SMC cells is remarkable (FIG. 11). In particular, these non-functionalized surface-based SMC cells (cells N and AC) exhibit a capacity that increases the number of cycles after slight degradation during the first 300 cycles. This is quite unique and unexpected. This is never obtained by conventional supercapacitors, lithium ion capacitors, lithium ion batteries, lithium super batteries or functionalized surface control cells.

In summary, the present invention provides an energy storage device having aspects of both a super capacitor and a lithium ion battery. These fully surfaceable lithium ion exchange cells can already store an energy density of at least 160 Wh / kg _cell , which is essentially higher than that of conventional electric double layer (EDL) supercapacitors. The power density of at least 100 kW / kg _cell is inherently higher than that of a conventional EDL supercapacitor and much higher than that of a conventional lithium ion battery. These surface-mediated cells can be quickly recharged for use as a conventional lithium ion battery.

  Although the invention has been described in detail and with reference to specific embodiments thereof, many variations and modifications can be made without departing from the spirit and scope of the invention as defined by the following claims. Will be clear.

Claims (32)

(A) a cathode comprising a cathode active material having a surface area capable of taking up or storing lithium therein;
(B) an anode comprising an anode active material having a surface area capable of taking up or storing lithium therein;
(C) a porous separator disposed between the two electrodes;
(D) comprising a lithium-containing electrolyte in physical contact with the two electrodes,
The anode active material and / or the cathode active material has a specific surface area of 100 m ² / g or more that is in direct physical contact with the electrolyte to receive or provide lithium ions thereto. ,
One or both of the anode active material and the cathode active material are functionalized, and at least one of the two electrodes includes a lithium source prior to the first charge or first discharge cycle of the energy storage device. Surface mediated lithium ion exchange energy storage device.   The energy storage device of claim 1, wherein the cathode active material is not a functionalized material.   The energy storage device of claim 1, wherein the device has an open circuit voltage of at least 0.6 volts.   When the device is in a charged state, at least 80% of the lithium is stored on the surface of the anode active material and is in direct contact with the anode surface, and when the device is in a discharged state, the The energy storage device of claim 1, wherein at least 80% of the lithium is stored on the surface of the cathode active material and is in direct contact with the cathode surface.   The energy storage device according to claim 1, wherein the electrolyte is a liquid electrolyte or a gel electrolyte containing an initial amount of lithium ions.   The energy storage device according to claim 1, wherein at least one active material of the two electrodes has a functional group that reversibly reacts with a lithium atom or an ion.   The energy storage device according to claim 6, wherein the anode active material and the cathode active material are functionalized with a functional group that reversibly reacts with lithium atoms or ions.   The energy storage device of claim 1, wherein the anode active material is not intercalated or deintercalated with lithium when the device is in operation.   The energy storage device of claim 1, wherein the device operates in a voltage range of 1.0 volts to 4.5 volts. 2. The energy storage device according to claim 1, wherein at least one of the two electrodes has a specific surface area in direct contact with the electrolyte of 500 m ² / g or more.   When the device is in a charged state, no more than 20% of the lithium is stored in the bulk of the anode active material, and when the device is in a discharged state, no more than 20% of the lithium is The energy storage device of claim 1, wherein the energy storage device is stored in a bulk of the cathode active material.   The energy storage device according to claim 1, wherein the operation of the device does not include lithium intercalation or deintercalation.   The energy storage device of claim 1, wherein the anode active material is pretreated with lithium. The anode active material is
(A) a porous irregular carbon material selected from soft carbon, hard carbon, polymerizable carbon or carbonized resin, mesofuse carbon, coke, carbonized pitch, carbon black, activated carbon or partially graphitized carbon;
(B) Graphene selected from graphene single-layer sheets or multilayer platelets, graphene oxide, graphene fluoride, graphene hydroxide, graphene nitride, boron-doped graphene, nitrogen-top graphene, or chemically or thermally reduced graphene oxide material,
(C) Exfoliated graphite,
(D) mesoporous carbon,
(E) a carbon nanotube selected from single-walled carbon nanotubes or multi-walled carbon nanotubes,
(F) carbon nanofibers, metal nanowires, metal oxide nanowires or fibers, or conductive polymer nanofibers,
(G) a carbonyl-containing courage or polymerizable molecule,
(H) a functionalized graphene material containing a carbonyl group, a carboxyl group or an amino group,
(I) The energy storage device according to claim 1, wherein the energy storage device is selected from a combination thereof. The cathode active material is
(A) a porous irregular carbon material selected from soft carbon, hard carbon, polymerizable carbon or carbonized resin, mesofuse carbon, coke, carbonized pitch, carbon black, activated carbon or partially graphitized carbon;
(B) a graphene material selected from a single layer sheet or multilayer platelet of graphene, graphene oxide, graphene fluoride, graphene hydroxide, graphene nitride, boron-doped graphene, nitrogen-topped graphene, functionalized graphene or reduced graphene oxide,
(C) Exfoliated graphite,
(D) mesoporous carbon,
(E) a carbon nanotube selected from single-walled carbon nanotubes or multi-walled carbon nanotubes,
(F) carbon nanofibers, metal nanowires, metal oxide nanowires or fibers, or conductive polymer nanofibers,
(G) a combination of these,
(H) a carbonyl-containing courage or polymerizable molecule,
(I) a functionalized graphene containing a carbonyl group, a carboxyl group or an amino group,
(J) The energy storage device according to claim 1, wherein the energy storage device is selected from these combinations.   The energy storage device according to claim 15, wherein the anode active material or the cathode active material is a graphene material having no functional group. Functional materials are poly (2,5-hydroxy-1,4-benzoquinone-3,6-methylene), Li _x C ₆ O ₆ (x = 1 to 3), Li ₂ (C ₆ H ₂ O ₄ ). , Li ₂ C ₈ H ₄ O ₄ (Li terephthalate), Li ₂ C ₆ H ₄ O ₄ (Li trans-trans-muconate), 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) sulfide Polymer, PTCDA, 1,4,5,8, -naphthalene-tetracarboxylic dianhydride (NTCDA), benzene-1,2,4,5-tetracarboxylic dianhydride, 1,4,5,8 16. The energy storage device according to claim 15, wherein the energy storage device is selected from the group consisting of: -tetraanhydranthraquinone, tetraanhydro-p-benzoquinone and combinations thereof. Functional materials are poly (2,5-hydroxy-1,4-benzoquinone-3,6-methylene), Li _x C ₆ O ₆ (x = 1 to 3), Li ₂ (C ₆ H ₂ O ₄ ). , Li ₂ C ₈ H ₄ O ₄ (Li terephthalate), Li ₂ C ₆ H ₄ O ₄ (Li trans-trans-muconate), 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) sulfide Polymer, PTCDA, 1,4,5,8, -naphthalene-tetracarboxylic dianhydride (NTCDA), benzene-1,2,4,5-tetracarboxylic dianhydride, 1,4,5,8 -Selected from the group of tetraanhydroanthraquinone, tetraanhydro-p-benzoquinone and combinations thereof, this functional material comprising nanographene, carbon nanotubes, disordered carbon, nanographs Ito, metal nanowires, conductive nanowires, carbon nanofibers, energy storage device according to claim 15, characterized in that it is supported by the combination with nanostructured material selected from a polymerizable nanofibers or nanostructured material.   The anode active material or the cathode active material may be pure graphene, graphene fluoride, graphene hydroxide, graphene nitride, boron-doped graphene, nitrogen-doped graphene, or a single-layer sheet or multilayer of chemically or thermally reduced graphene oxide The energy storage device according to claim 16, wherein the energy storage device is a non-functionalized graphene material selected from platelets.   The energy storage device according to claim 1, wherein at least one of the active materials is a single-walled or multi-walled carbon nanotube. According at least one of the functional material, R is a hydrocarbon, the _{-COOH, = O, -NH 2,} -OR, -COOR, and having a functional group selected from these combinations Item 4. The energy storage device according to Item 1.   The irregular carbon material is formed from two phases, a first phase that is a stack of graphite crystals or graphene surfaces, and a second phase that is amorphous carbon, and the first phase is dispersed in the second phase or The energy storage device according to claim 14, wherein the energy storage device is combined by a second phase.   The anode active material or the cathode active material is a non-functionalized single-walled or multi-walled carbon nanotube (CNT), oxidized CNT, fluorinated CNT, hydroxylated CNT, nitrided CNT, boron-doped CNT, nitrogen-doped CNT or doped CNT. The energy storage device according to claim 1, wherein the energy storage device is provided.   The energy storage device according to claim 1, wherein the electrolyte includes a lithium salt-doped ionic liquid.   The energy storage device according to claim 1, wherein the device provides an energy density of 300 Wh / kg or more and a power density of 5 kW / kg or more based on the total weight of the electrodes.   The energy storage device according to claim 2, wherein the uptake or storage at the electrode comprises an interaction with a graphene body on the surface of the active material.   27. The energy storage device according to claim 26, wherein the electrode is a cathode.   Providing a lithium source to the anode and ionizing the lithium source to release lithium ions into the electrolyte during the first discharge cycle of the device, or during the first charge cycle of the device; Providing a lithium source to the cathode and operating the lithium source to release lithium ions into the electrolyte, wherein both charging and discharging of the device do not involve lithium intercalation or solid diffusion The method of operating an energy storage device according to claim 1. (A) preparing a surface intervening cell comprising an anode, a lithium source, a porous separator, an electrolyte containing an initial amount of lithium ions, and a cathode;
(B) releasing lithium ions into the electrolyte from the lithium source during an initial discharge of the device;
(C) capturing lithium ions from the electrolyte at the cathode and storing the lithium captured on the cathode surface;
(D) exchanging more lithium ions than the initial amount between the lithium uptake surface of the anode and the lithium uptake surface of the cathode during successive charge or discharge operations;
The anode and the cathode comprise a material having a lithium uptake surface in contact with the electrolyte;
30. The method of claim 28, wherein the charging operation does not include lithium intercalation.   The energy storage device of claim 1, wherein the device has an open circuit voltage of at least 1.5 volts. The energy storage device of claim 1, wherein the anode includes an anode active material having a surface area in direct contact with the electrolyte of 500 m ² / g or more. The energy storage device according to claim 1, wherein at least one of the two electrodes has a surface area in direct contact with the electrolyte of 1,500 m ² / g or more.

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