Specific energy | 10–20 Wh/kg (36–72 J/g) |
---|---|
Energy density | 15–25 Wh/L (54–65 kJ/L) |
Energy efficiency | 75–90% [1] [2] |
Time durability | 20–30 years |
Cycle durability | >12,000–14,000 cycles [3] |
Nominal cell voltage | 1.15–1.55 V |
The vanadium redox battery (VRB), also known as the vanadium flow battery (VFB) or vanadium redox flow battery (VRFB), is a type of rechargeable flow battery. It employs vanadium ions as charge carriers. [5] The battery uses vanadium's ability to exist in a solution in four different oxidation states to make a battery with a single electroactive element instead of two. [6] For several reasons, including their relative bulkiness, vanadium batteries are typically used for grid energy storage, i.e., attached to power plants/electrical grids. [7]
Numerous companies and organizations are involved in funding and developing vanadium redox batteries.
Pissoort mentioned the possibility of VRFBs in the 1930s. [8] NASA researchers and Pellegri and Spaziante followed suit in the 1970s, [9] but neither was successful. Maria Skyllas-Kazacos presented the first successful demonstration of an All-Vanadium Redox Flow Battery employing dissolved vanadium in a solution of sulfuric acid in the 1980s. [10] [11] [12] Her design used sulfuric acid electrolytes, and was patented by the University of New South Wales in Australia in 1986. [2]
One of the important breakthroughs achieved by Skyllas-Kazacos and coworkers was the development of a number of processes to produce vanadium electrolytes of over 1.5 M concentration using the lower cost, but insoluble vanadium pentoxide as starting material. These processes involved chemical and electrochemical dissolution and were patented by the University of NSW in 1989. During the 1990s the UNSW group conducted extensive research on membrane selection, [13] [14] graphite felt activation, [15] [16] conducting plastic bipolar electrode fabrication, [17] electrolyte characterisation and optimisation as well as modelling and simulation. Several 1-5 kW VFB prototype batteries were assembled and field tested in a Solar House in Thailand and in an electric golf cart at UNSW. [18]
The UNSW All-Vanadium Redox Flow Battery patents and technology were licensed to Mitsubishi Chemical Corporation and Kashima-Kita Electric Power Corporation in the mid-1990s and subsequently acquired by Sumitomo Electric Industries where extensive field testing was conducted in a wide range of applications in the late 1990s and early 2000s. [19]
In order to extend the operating temperature range of the battery and prevent precipitation of vanadium in the electrolyte at temperatures above 40oC in the case of V(V), or below 10oC in case of the negative half-cell solution, Skyllas-Kazacos and coworkers tested hundreds of organic and inorganic additives as potential precipitation inhibitors. They discovered that inorganic phosphate and ammonium compounds were effective in inhibiting precipitation of 2 M vanadium solutions in both the negative and positive half-cell at temperatures of 5 and 45 °C respectively and ammonium phosphate was selected as the most effective stabilising agent. Ammonium and phosphate additives were used to prepare and test a 3 M vanadium electrolyte in a flow cell with excellent results. [19]
VRFBs' main advantages over other types of battery: [21]
VRFBs' main disadvantages compared to other types of battery: [21]
The electrodes in a VRB cell are carbon based. Several types of carbon electrodes used in VRB cell have been reported such as carbon felt, carbon paper, carbon cloth, and graphite felt. [25] [26] [27] Carbon-based materials have the advantages of low cost, low resistivity and good stability. Among them, carbon felt and graphite felt are preferred because of their enhanced three-dimensional network structures and higher specific surface areas, as well as good conductivity and chemical and electrochemical stability. [28] [29] The pristine carbon-based electrode exhibits hydrophobicity and limited catalytic activity when interacting with vanadium species. To enhance its catalytic performance and wettability, several approaches have been employed, including thermal treatment, acid treatment, electrochemical modification, and the incorporation of catalysts. [27] [30] Carbon felt is typically produced by pyrolyzing polyacrylonitrile (PAN) or rayon fibers at approximately 1500 °C and 1400 °C, respectively. Graphite felt, on the other hand, undergoes pyrolysis at a higher temperature of about 2400 °C. To thermally activate the felt electrodes, the material is heated to 400 °C in an air or oxygen-containing atmosphere. This process significantly increases the surface area of the felt, enhancing it by a factor of 10. [31] The activity towards vanadium species are attribute to the increase in oxygen functional groups such as carbonyl group (C=O) and carboxyl group (C-O) after thermal treatment in air. [32] There is currently no consensus regarding the specific functional groups and reaction mechanisms that dictate the interaction of vanadium species on the surface of the electrode. It has been proposed that the V(II)/V(III) reaction follows an inner-sphere mechanism, while the V(IV)/V(V) reaction tends to proceed through an outer-sphere mechanism. [30]
Both electrolytes are vanadium-based. The electrolyte in the positive half-cells contains VO+2 and VO2+ ions, while the electrolyte in the negative half-cells consists of V3+ and V2+ ions. The electrolytes can be prepared by several processes, including electrolytically dissolving vanadium pentoxide (V2O5) in sulfuric acid (H2SO4). [33] The solution is strongly acidic in use.
The membrane should allow protons to cross while keeping electrons and other ions separate. This creates charge separation and thus voltage. The most common membrane material is perfluorinated sulfonic acid (PFSA or Nafion). However, vanadium ions can penetrate a PFSA membrane, a phenomenon known as crossing-over, reducing the energy capacity of the battery. [34] [35] A 2021 study found that penetration is reduced with hybrid sheets made by growing tungsten trioxide nanoparticles on the surface of single-layered graphene oxide sheets. These hybrid sheets are then embedded into a sandwich structured PFSA membrane reinforced with polytetrafluoroethylene (Teflon). The nanoparticles also promote proton transport, offering high coulombic efficiency and energy efficiency of more than 98.1 percent and 88.9 percent, respectively. [36]
The resistive losses identified by the polarisation curve can be attributed to three main areas: activation loss, ohmic loss, and mass transport loss. Activation loss arises from slow charge transfer kinetics between the surface of the electrode and electrolyte. Ohmic losses are from the ohmic resistance of the electrolyte, electrode, membrane, and current collector. Ohmic losses can be reduced by improved cell design, such as zero-gap cell design and reduced membrane thickness. [37] Mass transport losses are from the lack of active vanadium species being transported to the electrode surface. The flow field design that promotes convective mass transport is crucial to reducing mass transport losses. [38] [39] Serpentine and interdigitated flow field designs were produced by machining a bipolar plate adjacent to the porous electrode. The felt electrode can also be cut to create an electrolyte flow channel. [40] [41] Both serpentine and interdigitated flow fields have been shown to enhance mass transport, which reduces mass transport polarisation and therefore increases limiting current density and peak power density. Flow dispensers are sometimes placed in the cell to distribute the flow and reduce jets. The flow field must also be designed to provide uniform electrolyte distribution to prevent dead zones in the cell and reduce pressure drop across the cell stack. [41] [42]
The reaction uses the half-reactions: [43]
Other useful properties of vanadium flow batteries are their fast response to changing loads and their overload capacities. They can achieve a response time of under half a millisecond for a 100% load change, and allow overloads of as much as 400% for 10 seconds. Response time is limited mostly by the electrical equipment. Unless specifically designed for colder or warmer climates, most sulfuric acid-based vanadium batteries work between about 10 and 40 °C. Below that temperature range, the ion-infused sulfuric acid crystallizes. [46] Round trip efficiency in practical applications is around 70–80%. [47]
The original VRFB design by Skyllas-Kazacos employed sulfate (added as vanadium sulfate(s) and sulfuric acid) as the only anion in VRFB solutions, which limited the maximum vanadium concentration to 1.7 M of vanadium ions. [48] In the 1990s, Skyllas-Kazacos discovered the use of ammonium phosphate and other inorganic compounds as precipitation inhibitors to stabilise 2 M vanadium solutions over a temperature range of 5 to 45 oC and a Stabilising Agent patent was filed by UNSW in 1993. This discovery was largely overlooked however and in around 2010 a team from Pacific Northwest National Laboratory proposed a mixed sulfate-chloride electrolyte, that allowed for the use in VRFBs solutions with the vanadium concentration of 2.5 M over a whole temperature range between −20 and +50 °C. [49] [50] Based on the standard equilibrium potential of the V5+/V4+ couple it is expected to oxidize chloride, and for this reason chloride solutions were avoided in earlier VRFB studies. The surprising oxidative stability (albeit only at the state of charge below ca. 80%) of V5+ solutions in the presence of chloride was explained on the basis of activity coefficients. [51] Many researchers explain the increased stability of V(V) at elevated temperatures by the higher proton concentration in the mixed acid electrolyte that shifts the thermal precipitation equilibrium of V(V) away from V2O5. Nevertheless, because of a high vapor pressure of HCl solutions and the possibility of chlorine generation during charging, such mixed electrolytes have not been widely adopted. [52]
Another variation is the use of vanadium bromide salts. Since the redox potential of Br2/2Br- couple is more negative than that of V5+/V4+, the positive electrode operates via the bromine process. [53] However, due to problems with volatility and corrosivity of Br2, they did not gain much popularity (see zinc-bromine battery for a similar problem). A vanadium/cerium flow battery has also been proposed . [54]
VRBs achieve a specific energy of about 20 Wh/kg (72 kJ/kg) of electrolyte. Precipitation inhibitors can increase the density to about 35 Wh/kg (126 kJ/kg), with higher densities possible by controlling the electrolyte temperature. The specific energy is low compared to other rechargeable battery types (e.g., lead–acid, 30–40 Wh/kg (108–144 kJ/kg); and lithium ion, 80–200 Wh/kg (288–720 kJ/kg)).[ citation needed ]
VRFBs' large potential capacity may be best-suited to buffer the irregular output of utility-scale wind and solar systems. [21]
Their reduced self-discharge makes them potentially appropriate in applications that require long-term energy storage with little maintenance—as in military equipment, such as the sensor components of the GATOR mine system. [55] [21]
They feature rapid response times well suited to uninterruptible power supply (UPS) applications, where they can replace lead–acid batteries or diesel generators. Fast response time is also beneficial for frequency regulation. These capabilities make VRFBs an effective "all-in-one" solution for microgrids, frequency regulation and load shifting. [21]
Name | Commissioning date | Energy (MWh) | Power (MW) | Duration (hours) | Country |
---|---|---|---|---|---|
Minami Hayakita Substation [56] [57] | December 2015 | 60 | 15 | 4 | Japan |
Pfinztal, Baden-Württemberg [58] [59] [60] | September 2019 | 20 | 2 | 10 | Germany |
Woniushi, Liaoning [61] [62] | 10 | 5 | 2 | China | |
Tomamae Wind Farm [63] | 2005 | 6 | 4 | 1:30 | Japan |
Zhangbei Project [64] | 2016 | 8 | 2 | 4 | China |
SnoPUD MESA 2 Project [65] [66] | March 2017 | 8 | 2 | 4 | USA |
San Miguel Substation [67] | 2017 | 8 | 2 | 4 | USA |
Pullman Washington [68] | April 2015 | 4 | 1 | 4 | USA |
Dalian Battery [69] | October 2022 | 400 (800) | 100 (200) | 4 | China |
Companies funding or developing vanadium redox batteries include Sumitomo Electric Industries, [70] CellCube (Enerox), [71] UniEnergy Technologies, [72] StorEn Technologies [73] [74] in Australia, Largo Energy [75] and Ashlawn Energy [76] in the United States; H2 in Gyeryong-si, South Korea; [77] Renewable Energy Dynamics Technology, [78] Invinity Energy Systems [79] in the United Kingdom, VoltStorage [80] and Schmalz [81] [82] in Europe; Prudent Energy [83] in China; Australian Vanadium, CellCube and North Harbour Clean Energy [84] [85] in Australia; Yadlamalka Energy Trust and Invinity Energy Systems [86] [87] in Australia; EverFlow Energy JV SABIC SCHMID Group in Saudi Arabia [88] and Bushveld Minerals in South Africa. [89]
An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit. Electrodes are essential parts of batteries that can consist of a variety of materials (chemicals) depending on the type of battery.
An electrochemical cell is a device that generates electrical energy from chemical reactions. Electrical energy can also be applied to these cells to cause chemical reactions to occur. Electrochemical cells that generate an electric current are called voltaic or galvanic cells and those that generate chemical reactions, via electrolysis for example, are called electrolytic cells.
In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from naturally occurring sources such as ores using an electrolytic cell. The voltage that is needed for electrolysis to occur is called the decomposition potential. The word "lysis" means to separate or break, so in terms, electrolysis would mean "breakdown via electricity."
A lithium-ion or Li-ion battery is a type of rechargeable battery that uses the reversible intercalation of Li+ ions into electronically conducting solids to store energy. In comparison with other commercial rechargeable batteries, Li-ion batteries are characterized by higher specific energy, higher energy density, higher energy efficiency, a longer cycle life, and a longer calendar life. Also noteworthy is a dramatic improvement in lithium-ion battery properties after their market introduction in 1991: over the following 30 years, their volumetric energy density increased threefold while their cost dropped tenfold.
A rechargeable battery, storage battery, or secondary cell, is a type of electrical battery which can be charged, discharged into a load, and recharged many times, as opposed to a disposable or primary battery, which is supplied fully charged and discarded after use. It is composed of one or more electrochemical cells. The term "accumulator" is used as it accumulates and stores energy through a reversible electrochemical reaction. Rechargeable batteries are produced in many different shapes and sizes, ranging from button cells to megawatt systems connected to stabilize an electrical distribution network. Several different combinations of electrode materials and electrolytes are used, including lead–acid, zinc–air, nickel–cadmium (NiCd), nickel–metal hydride (NiMH), lithium-ion (Li-ion), lithium iron phosphate (LiFePO4), and lithium-ion polymer.
A flow battery, or redox flow battery, is a type of electrochemical cell where chemical energy is provided by two chemical components dissolved in liquids that are pumped through the system on separate sides of a membrane. Ion transfer inside the cell occurs across the membrane while the liquids circulate in their respective spaces.
Electrolysis of water is using electricity to split water into oxygen and hydrogen gas by electrolysis. Hydrogen gas released in this way can be used as hydrogen fuel, but must be kept apart from the oxygen as the mixture would be extremely explosive. Separately pressurised into convenient 'tanks' or 'gas bottles', hydrogen can be used for oxyhydrogen welding and other applications, as the hydrogen / oxygen flame can reach approximately 2,800°C.
A zinc-bromine battery is a rechargeable battery system that uses the reaction between zinc metal and bromine to produce electric current, with an electrolyte composed of an aqueous solution of zinc bromide. Zinc has long been used as the negative electrode of primary cells. It is a widely available, relatively inexpensive metal. It is rather stable in contact with neutral and alkaline aqueous solutions. For this reason, it is used today in zinc–carbon and alkaline primaries.
The polysulfide–bromine battery is a type of rechargeable electric battery that stores electrical energy in liquids, such as water-based solutions of two salts: sodium bromide and sodium polysulfide. It is a type of redox (reduction–oxidation) flow battery.
The lithium–air battery (Li–air) is a metal–air electrochemical cell or battery chemistry that uses oxidation of lithium at the anode and reduction of oxygen at the cathode to induce a current flow.
Zinc–cerium batteries are a type of redox flow battery first developed by Plurion Inc. (UK) during the 2000s. In this rechargeable battery, both negative zinc and positive cerium electrolytes are circulated though an electrochemical flow reactor during the operation and stored in two separated reservoirs. Negative and positive electrolyte compartments in the electrochemical reactor are separated by a cation-exchange membrane, usually Nafion (DuPont). The Ce(III)/Ce(IV) and Zn(II)/Zn redox reactions take place at the positive and negative electrodes, respectively. Since zinc is electroplated during charge at the negative electrode this system is classified as a hybrid flow battery. Unlike in zinc–bromine and zinc–chlorine redox flow batteries, no condensation device is needed to dissolve halogen gases. The reagents used in the zinc-cerium system are considerably less expensive than those used in the vanadium flow battery.
A supercapacitor (SC), also called an ultracapacitor, is a high-capacity capacitor, with a capacitance value much higher than solid-state capacitors but with lower voltage limits. It bridges the gap between electrolytic capacitors and rechargeable batteries. It typically stores 10 to 100 times more energy per unit volume or mass than electrolytic capacitors, can accept and deliver charge much faster than batteries, and tolerates many more charge and discharge cycles than rechargeable batteries.
A hydrogen–bromine battery is a rechargeable flow battery in which hydrogen bromide (HBr) serves as the system’s electrolyte. During the charge cycle, as power flows into the stack, H2 is generated and stored in a separate tank, the other product of the chemical reaction is HBr3 which accumulates in the electrolyte. During the discharge cycle the H2 is combined again with the HBr3 and the system returns to its initial stage with a full tank of HBr. The electrolyte suffers no degradation during the process and the system is self contained with no emissions.
Pseudocapacitance is the electrochemical storage of electricity in an electrochemical capacitor that occurs due to faradaic charge transfer originating from a very fast sequence of reversible faradaic redox, electrosorption or intercalation processes on the surface of suitable electrodes. Pseudocapacitance is accompanied by an electron charge-transfer between electrolyte and electrode coming from a de-solvated and adsorbed ion. One electron per charge unit is involved. The adsorbed ion has no chemical reaction with the atoms of the electrode since only a charge-transfer takes place. Supercapacitors that rely primarily on pseudocapacitance are sometimes called pseudocapacitors.
Research in lithium-ion batteries has produced many proposed refinements of lithium-ion batteries. Areas of research interest have focused on improving energy density, safety, rate capability, cycle durability, flexibility, and reducing cost.
A solid dispersion redox flow battery is a type of redox flow battery using dispersed solid active materials as the energy storage media. The solid suspensions are stored in energy storage tanks and pumped through electrochemical cells while charging or discharging. In comparison with a conventional redox flow battery where active species are dissolved in aqueous or organic electrolyte, the active materials in a solid dispersion redox flow battery maintain the solid form and are suspended in the electrolyte. Further development expanded the applicable active materials. The solid active materials, especially with active materials from lithium-ion battery, can help the suspensions achieve much higher energy densities than conventional redox flow batteries. This concept is similar to semi-solid flow batteries in which slurries of active materials accompanied by conductive carbon additives to facilitate electrons conducting are stored in energy storage tanks and pumped through the electrochemical reaction cells. Based upon this technique, an analytical method was developed to measure the electrochemical performance of lithium-ion battery active materials, named dispersed particle resistance (DPR).
Maria Skyllas-Kazacos is an Australian chemical engineer best known for her pioneering work of the vanadium redox battery, which she created at the University of New South Wales in the 1980s. Her design used sulfuric acid electrolytes and was patented by the university. In 1999 she was appointed a Member of the Order of Australia "for service to science and technology, particularly in the development of the vanadium redox battery as an alternative power source".
A semi-solid flow battery is a type of flow battery using solid battery active materials or involving solid species in the energy carrying fluid. A research team in MIT proposed this concept using lithium-ion battery materials. In such a system, both positive (cathode) and negative electrode (anode) consist of active material particles with carbon black suspended in liquid electrolyte. Active material suspensions are stored in two energy storage tanks. The suspensions are pumped into the electrochemical reaction cell when charging and discharging. This design takes advantage of both the designing flexibility of flow batteries and the high energy density active materials of lithium-ion batteries.
This is a history of the lithium-ion battery.
The Iron Redox Flow Battery (IRFB), also known as Iron Salt Battery (ISB), stores and releases energy through the electrochemical reaction of iron salt. This type of battery belongs to the class of redox-flow batteries (RFB), which are alternative solutions to Lithium-Ion Batteries (LIB) for stationary applications. The IRFB can achieve up to 70% round trip energy efficiency. In comparison, other long duration storage technologies such as pumped hydro energy storage provide around 80% round trip energy efficiency.